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.

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.

scholarly journals 1-[4-{1,1′,1″,1‴,1′′′′-(1,3-Cyclopentadien-1,2,3,4,5-pentayl)pentakis}]-(4,1-phenylen)-alkanone und -benzoesäure pentaalkylester und deren Natrium- und Thallium(I)-Komplexe / 1-[4-{1,1′,1″,1‴,1′′′′-( 1,3-Cyclopentadiene-1,2,3,4,5-pentayl)pentakis}]-(4,1-phenylene)-alkanones and -benzoic Acid Pentaalkyl Esters and their Sodium- and Thallium(I) Complexes

1992 ◽  
Vol 47 (9) ◽  
pp. 1281-1289 ◽  
Author(s):  
Herbert Schumann ◽  
Homa Kucht ◽  
Andreas Kucht
Keyword(s):  
Benzoic Acid ◽  
Nmr Spectra ◽  
Sodium Salts ◽  
Acyl Chlorides ◽  
New Compounds ◽  
C Nmr

Pentaphenylcyclopentadiene (1) reacts with acyl chlorides RC(O)Cl (R = CH3, C3H7, C5H11, C7H15) with formation of the corresponding [(cyclopentadiene pentayl)pentakis] (1,4-phenylene) alkanones C5H(C6H4C(O)R-4)5 (2a, 2c, 2d and 2e). 2 a reacts with KOCl in water/dioxane to yield C5Cl(C6H4C(O)OH-4)5 (3), which after reaction with C2H5OH and C5H11OH gives the pentaesters C5Cl(C6H4C(O)OR-4)5 (4b and 4d), and after reaction with (CH3)3SnH the corresponding [(cyclopentadiene pentayl)pentakis] benzoic acid pentaalkyl esters C5H(C6H4C(O)OR-4)5 (5b and 5d). Reaction of 2a, 2c, 2d, 2e and 5b with NaNH2 results in the formation of the sodium salts Na[C5(C6H4C(O)R-4)5] (6a, 6c, 6d and 6e) and Na[C5(C6H4C(O)OC2H5-4)5] (7). 2a, 2c, 2d, 2e, 5b and 5d react with TlOC2H5 to give the thallium(I) derivatives Tl[C5(C6H4C(O)R-4)5] (8a, 8c, 8d, 8e) and Tl[C5(C6H4C(O)OR-4)5] (9b and 9d). The 1H and 13C NMR spectra of the new compounds are reported and discussed.

Spectroscopic Studies with N-Chloroarylsulphonamides: IR and 1H, 13C and 23Na Nmr Spectra of Sodium Salts of N-Chloro-Mono- and Di-Substituted-Benzenesulphonamides, 4-X-C6H4SO2NANCl (X = H; CH3; C2H5; F; Cl; Br; I or NO2) and i-X, j-YC6H3SO2NANCl (i-X, j-Y = 2,3-(CH3)2; 2,4-(CH3)2; 2,5-(CH3)2; 2-CH3, 4-Cl; 2-CH3, 5-Cl; 3-CH3, 4-Cl; 2,4-Cl2 or 3,4-Cl2)

2003 ◽  
Vol 58 (1) ◽  
pp. 51-56 ◽  
Author(s):  
◽  
J. D. D’Souza ◽  
B. H. Arun Kumar
Keyword(s):  
Solid State ◽  
Chemical Shift ◽  
Infrared Spectra ◽  
Phenyl Ring ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Spectroscopic Studies ◽  
Sodium Salts ◽  
Experimental Chemical Shift ◽  
23Na Nmr

In an effort to introduce N-chloroarylsulphonamides of different oxydising strengths, sixteen sodium salts of N-chloro-mono- and di-substituted benzenesulphonamides of the configuration, 4- X-C6H4SO2NaNCl (where X = H; CH3; C2H5; F; Cl; Br; I or NO2) and i-X, j-YC6H3SO2NaNCl (where i-X, j-Y = 2,3-(CH3)2; 2,4-(CH3)2; 2,5-(CH3)2; 2-CH3,4-Cl; 2-CH3,5-Cl; 3-CH3,4-Cl; 2,4- Cl2 or 3,4-Cl2) are prepared, characterized through their infrared spectra in the solid state and NMR spectra in solution. The υN-Cl frequencies vary in the range 950 - 927 cm−1. Effects of substitution in the benzene ring in terms of electron donating and electron withdrawing groups have been considered, and conclusions drawn. The chemical shifts of aromatic protons and carbon-13 in all the N-chloroarylsulphonamides have been calculated by adding substituent contributions to the shift of benzene. Considering the approximation employed the agreement between the calculated and experimental chemical shift values for different protons or carbon-13 is quite good. Effects of phenyl ring substitution on chemical shift values of both 1H and 13C are also graphically represented in terms of line diagrams.

Some alkali metal alkyl amides as alkyne isomerization reagents: selective isomerization of one triple bond of a diynol

1983 ◽  
Vol 61 (6) ◽  
pp. 1073-1076 ◽  
Author(s):  
Suzanne R. Abrams ◽  
Donato D. Nucciarone ◽  
Warren F. Steck
Keyword(s):  
Sex Pheromone ◽  
Alkali Metal ◽  
Sodium Salt ◽  
Triple Bond ◽  
Lithium Salt ◽  
Terminal Position ◽  
Sodium Salts ◽  
Triple Bonds ◽  
High Yields ◽  
Insect Sex

The lithium and sodium salts of 1,2-diaminoethane, 1,3-diaminopropane, n-butylamine, and the lithium salt of isobutylamine were studied as potential reagents for isomerization of triple bonds in alkyn-1-ols. The sodium salts of the diamines afforded high yields of the ω-alkyn-1-ol. Somewhat surprisingly, the sodium salt of n-butylamine also effects isomerization to the terminal position. The lithium salt of 1,3-diaminopropane gave the highest conversion of 2- to 3-alkyn-1-ol. A novel, selective rearrangement of one triple bond of a diynol, a 2, ω- to 3, ω-diyn-1-ol isomerization, was incorporated into a synthesis of the insect sex pheromone 3,13-octadecadienol acetate.

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.

Direct NMR evidence for the equivalent participation of L-phenylalanine and L-tyrosine in the biosynthesis of the intermolecular Diels–Alder type adducts of prenylchalcone and prenylated 2-arylbenzofuran in Morus alba cell cultures

1994 ◽  
Vol 72 (1) ◽  
pp. 12-14 ◽  
Author(s):  
Yoshio Hano ◽  
Taro Nomura ◽  
Shinichi Ueda
Keyword(s):  
Amino Acids ◽  
Cell Cultures ◽  
Nmr Spectra ◽  
Diels Alder ◽  
Morus Alba ◽  
High Yields ◽  
C Nmr

L-[3-13C]Phenylalanine and L-[3-13C]tyrosine were administered to Morus alba cell cultures, to produce intermolecular Diels–Alder type adducts of a prenylchalcone and a 2-arylbenzofuran such as chalcomoracin (1) as well as the adducts of two molecules of prenylchalcones such as kuwanon J (2) in high yields. The 13C NMR spectra of 1 and 2 isolated from the cultures revealed that both amino acids were incorporated intact into chalcomoracin (1) and kuwanon J (2). This is the first example of direct NMR evidence for the almost equivalent incorporation of phenylalanine and tyrosine into the shikimate metabolites. This finding suggests the participation of a biosynthetic route from phenylalanine via trans-cinnamate to p-coumarate and from tyrosine to p-coumarate in this plant.

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.

Sign in / Sign up

Export Citation Format

Share Document