Ba(OH)2 as catalyst in organic reactions, part XIV. Michael addition catalyzed by barium complex salts in the homogeneous phase

Michael addition to chalcone is catalyzed by barium complex salts in the homogeneous phase under various conditions. The nature of these intermediates is analyzed. These complex salts are described for the first time. The Michael adduct of malonodinitrile to chalcone is described for the first time.

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Dielectric constants of acetonitrile, γ-butyrolactone,propylene carbonate,and 1,2-dimethoxyethane as a function of pressure and temperature

The dielectric constants of 1,2-dimethoxyethane, acetonitrile, -butyrolactone, and propylene carbonate were determined from capacitance measurements extrapolated to infinite frequency; ln are reported as a function of pressure up to 80 MPa at 15, 25, 35, 45°C and as a function of temperature in the range 10 to 50°C at 0.10133 MPa. The variation of ln with temperature or pressure can be expressed by a second order polynomial expression. The isothermal compressibilities of the solvents were determined at 25°C from sound velocities, densities, and heat capacities. A simple correlation can be established between ln /P and for most aprotic solvent.     

Recent progress in tartaric acid‐modified Raney nickel system for enantio‐differentiating hydrogenation

Tartaric acidmodified Raney nickel (TAMRNi) is an enantiodifferentiating catalyst for hydrogenation of ketones. The stereochemical models explaining the enantiodifferentiation of ketoester and 2alkanone were unified as an extended stereochemical model by the experimental supports. Based on this new model, a working hypothesis to improve the enantiomeric excess (ee) of the ketoester/TAMRNi system was developed, and the ee was improved to 96%. By further fine tuning of this system, almost perfect enantiodifferentiation resulting in over 98% ee was achieved.     

Nitrosation of mefenorex in the presence of cyclodextrins

- and -Cyclodextrin (CD) and heptakis-2,6-di-O-methyl--cyclodextrin (DIMEB) form soluble inclusion compounds with mefenorex (MEF); with -CD a partial inclusion occurs. No solid inclusion compound could be obtained with the four CDs. -, -CD and DIMEB, but not -CD, enhance the nitrosation rate of MEF if the nitrosation assay procedure (NAP test) is applied. During this reaction with - and -CD, solid inclusion compounds of the CDs and nitrosomefenorex (NMEF) precipitate.Part of the Ph.D. thesis of V. Wedelich, Freie Universität Berlin, 1985.     

Inclusion of Ring A of Cholesterol Inside the β-Cyclodextrin Cavity: Evidence from Oxidation Reactions and Structural Studies

The disposition of cholesterol inside the -cyclodextrin cavity(-CD) was deduced from oxidation of cholesterol secondary alcoholgroups by Ca(OCl)₂ and H₂O₂ in thepyridine–acetic acid system. The amount of cholest-4-ene-3-one formedwas found to be proportional to the concentration of -cyclodextrin,resulting in 56.1% of ketone. The oxidation rate was enhanced by-cyclodextrin and its methyl, polymer and 1 : 1copper(II)–-cyclodextrin derivatives. Detailed investigationsinvolving UV-visible, ¹³C- and ¹H-NMR(T₁, 1D NOE and ROESY) spectroscopic studies were carried out.A binding constant value of 15,385 ± 1500 M^-2 wasobtained for the 2 : 1heptakis-2,6-di-O-methyl--cyclodextrin(DM-CD) : cholesterolcomplex in chloroform from UV studies. Proton and solid state¹³C-CP MAS spectra of the -CD–cholesterol mixtureshowed large magnitude shifts for the protons from the wider end of the-CD cavity as well as those of ring A and ring B of cholesterol. Both1D NOE and ROESY measurements indicated the proximity between ring A andring B protons of cholesterol and the wider end protons of -CD andDM-CD. Besides, analysis of _c,_i and tau;_m from T₁measurements showed not only a lowering of rotational motions but a value of 0.016–0.048 for some of the cholesterol protons, typical of aweak complex. Based on these studies, a probable structure for the 2 : 1complex involving two molecules of -CD/DM-CD was proposed withportions of ring A and ring B being present inside the wider end of the-CD/DM-CD cavity and ring D and the side chain attached atposition 17, projecting into the wider end of the secondCD/DM-CD molecule.     

Surface Tension and 1H NMR Studies on Inclusion Complexes of β-Cyclodextrin with Sodium Alkyl Sulfonate

The inclusion complexes of -CD with sodium octylsulfonate (C8As), sodium dodecyl sulfonate (C12As), andsodium hexadecyl sulfonate (C16As) in aqueous solutions havebeen studied by surface tension measurement at the air/water interfaceand 1H NMR spectroscopy at 323 K.At fixed concentrations of the surfactants, the surface tensions firstincrease with the increase of -CD concentrations,then they attain a maximum. The surface tension curves of the surfactantsin the presence of -CD are higher than those in the absence of-CD. The values increase with increasing -CD concentrations foreach surfactant. The apparent critical micelle concentrations (CMC) of thesurfactants vary linearly with -CD concentrations.A 1H NMR study shows that the signals of theinner H-3 and H-5 of -CDshift upfield upon addition of the surfactants.The magnitude of the chemicalshift changes (= CD obs)varies as a functionof the concentrations of the surfactants. From therelationships between the chemicalshift changes of H-3 or H-5 inside the -CD cavityand guest/host molar ratios, a 1:1 stoichiometry foreach inclusion complex is assumed. The associationconstants of the inclusion complexes have beendetermined by 1H NMR spectroscopy.     

Basic studies of the influence ofβ-cyclodextrin and 2-hydroxypropylβ-cyclodextrin on the photo-oxidation reaction of phenothiazine in inclusion complexes,using fluorescence detection

The photo-oxidation reaction of phenothiazine has been studied in the presence of-cyclodextrin (-CD) and 2-hydroxypropyl-cyclodextrin (HP -CD). The influence of these organized media on the formation of the oxidation photoproduct upon UV irradiation has been investigated. Phenothiazine forms an inclusion complex with the cyclodextrins. The stoichiometry and formation constant of the complex formed with 2-hydroxypropyl -CD have been calculated using the changes of the fluorescence emission signal and of the absorbance of the drug upon inclusion. An increase of the fluorescence intensity of the photogenerated product is attained when it becomes included inside the cyclodextrin cavity.     

Quantum-chemical study of allylic compounds with two bonded heavy atoms

It has been shown by the CNDO method that the bathochromic shift of the long-wave absorption band in the transition from allylstannane to compounds of the type C=C-C-Sn-X and C=C-Sn-X (where X is a heavy atom) is connected with the formation of a low-energy vacant *_S-X orbital, localized mainly in the region of the Sn-X chemical bond, and of an occupied _Sn-X orbital, the energy of which is somewhat higher than of the _C-Sn orbital. The dependence of the position of the long-wave absorbance region on conformation is related to the fact that, in planar and nonplanar conformers, the long-wave transitions are of a different type ( * and *, respectively); the bathochromic shift is determined to a large degree by the difference in the energies of the highest occupied MO ( - ) in the s-trans form. In the nonplanar conformers the heavy atom orbitals interact with the -orbital of the ethylene moiety through the bridge group; this leads to a significant delocalization of the HOMO and to a considerable change in its energy. On the other hand, their interaction with the *-orbital in compounds of the C=C-C-Sn-X type is very low and does not favor the delocalization of lower vacant MO. In vinyldistannane the *-orbital is noticeably delocalized, due to the interaction with the *_Sn-Sn orbital in planar and with the *_Sn-Sn orbital in nonplanar conformers.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 636–641, March, 1992.     

Sulfur heterocycles. 13. Oxidative chlorination of β-thiolactones. A novel synthesis of β-(chlorosulfinyl)alkanoyl chlorides and 1,2-oxathiolan-5-one 2-oxides

Chlorination of -thiolactones with chlorine or sulfuryl chloride in acetic anhydride at a reactant ratio (RR) of 1:2:1 gives -(chlorosulfinyl)alkanoyl chlorides in 75–89% yields. Oxidative chlorination of -thiolactones with RR of 1:3:2 affords -(chlorosulfinyl)alkanoyl chlorides and cyclic sulfinic anhydrides (1,2-oxathiolan-5-one 2-oxides). The optimum RR for the preparation of 1,2-oxathiolan-5-one 2-oxides is 1:2:2. Hydrolysis of -chloro--(chlorosulfinyl)carbonyl chlorides has given novel -chlorinated sulfinocarboxylic acids.For communication 12, see [1].A. N. Nesmeyanov Institute of Heteroorganic Chemistry, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2153–2158, September, 1992.     

Complex formation of some nonionic surfactants with hydroxypropyl-β-cyclodextrin and with heptakis (2,6-di-O-methyl)-β-cyclodextrin

The interaction of six nonionic surfactants -[4-(1,1,3,3-tetra-methylbutyl)phenyl]--hydroxypoly(oxy-1,2-ethanediyl) with hydroxypropyl--cyclodextrin (HPCD) and dimethyl--cyclodextrin (DIMEB) was studied by reversed-phase thin-layer chromatography in the presence and absence of sodium chloride. Each surfactant formed complexes with both cyclodextrin derivatives; however, the strength of interaction varied considerably. DIMEB formed more stable inclusion complexes with the surfactants than did HPCD. A longer ethyleneoxide chain decreased the strength of interaction, whereas sodium chloride exerted a negligible impact. Principal component analysis indicated that both the hydrophobicity and the specific hydrophobic surface are of the surfactant influenced the complex formation indicating the hydrophobic character of the interaction.Dedicated to Professor József Szejtli.     

Improvement of Solubility and Dissolution of 19-Norprogesterone via Inclusion Complexation

In an effort to modify the solubility and dissolution rate of the contraceptive steroid, 19-norprogesterone in order to improve its bioavailability, the cyclodextrin complexation approach was chosen. In solution, the complex formation with -cyclodextrin (-CD), hydroxyethyl -cyclodextrin (HE--CD) and hydroxypropyl -cyclodextrin (HP--CD) was confirmed by using solubility, UV, IR and ¹H-NMR spectrophotometric techniques. The phase solubility diagrams were categorized as A_L-type. The complexing affinity of the CDs investigated were ranked as follows: -CD > HP--CD > HE--CD. The complexation thermodynamic parameters were obtained from the temperature dependence of the dissociation constants. In the solid state, differential scanning calorimetery (DSC) and optical microscopy methods were utilized to characterize the complexes. Dissolution studies showed that such molecularly encapsulated forms offered a marked improvement in the dissolution rate compared to the parent drug.     

The resolution of some chiral compounds in reversed-phase high-performance liquid chromatography by means of β-cyclodextrin inclusion complexes

Summary -Cyclodextrin is applied as the chiral component of the mobile phase in a systematic study of the resolution —into enantiomers — of mandelic acid and its derivatives by reversed-phase liquid chromatography. It is found that the stereoselectivity arising from inclusion in -cyclodextrin molecules is significant (=1.02÷1.05) only for the compounds showing at the asymmetric carbon atom the presence of first, an intact carboxylic group and second, a functional group capable of hydrogen bonding with the hydroxyl groups of -cyclodextrin. Results are discussed in the light of the three-point attachment model of stereoselectivity as well as of the structure of the inclusion complexes.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Isolation of ovine β-lactoglobulin genetic variants by chromatofocusing: Heterogeneity of β-lactoglobulin A

Summary Chromatofocusing was applied to the isolation of ovine -Lactoglubulin (-Lg) genetic variants. Ovine -Lg A and B, which are known to differ only by a single amino-acid substitution, were separated. Moreover, one component differing from A variant in isoelectric point and relative molecular mass has been isolated in samples containing ovine -Lg A. Although elution of -Lgs occurred far from their normal isoelectric points, chromatofocusing is a powerful technique effective for both analytical and preparative scale.     

Triterpene Glycosides of Astragalus and Their Genins. LXI. Occurrence of Cycloartane 6-O-Monodesmosides

Cyclosiversigenin 6-O--L-rhamnopyranoside and 6-O--D-glucopyranoside were isolated fromAstragalus coluteocarpusBoiss. (Leguminosae) andAstragalus dissectusB. Fedtsch. et N. Ivanova, respectively. Cyclosiversigenin 5-O--L-rhamnopyranoside was shown to be an artifact forAstragalus coluteocarpus.Thus, the cyclosiversigenin 6-O--D-glucopyranoside that was isolated from certainAstragalusspecies is hypothesized also to be an artifact. Glycosylation of the 6 -hydroxyl group of cycloartanes by D-glucose and D-xylose, in contrast with other substituents, does not change the low-field position of the PMR signal of the 4-CH ₃ group (1.65 2.01 ppm) that is caused by the influence of deuteropyridine directly on the 6 -hydroxyl. Obviously one of the hydroxyls of the -D-glucopyranoside or -D-xylopyranoside residues has the same effect in this instance.     

Solubility Study of Nimodipine Inclusion Complexation with α- and β-Cyclodextrin and some Substituted Cyclodextrins

The solubility of nimodipine was measured in aqueous solutions of the following cyclodextrins: -cyclodextrin (-CD), hydroxypropyl--CD (HP--CD), -cyclodextrin (-CD), random substituted methyl--CD (M--CD), three hydroxypropyl--CDs (HP--CD) with mutually different average degree of substitution, and hydroxypropyl--cyclodextrin (HP--CD). From the determined linear solubility diagrams the values of the binding constant K₁₁ of the inclusion complexes of nimodipine with the respective CDs were evaluated. The -CDs efficiently solubilized sparingly soluble nimodipine, the highest value of K₁₁ was found for M--CD (1680 M^-1), followed by -CD (550 M^-1) and HP--CDs, where the higher degree of substitution lowered K₁₁. Only slight solubilization of nimodipine was observed in the solutions of the -CDs and HP--CD.     

Effect of Cyclodextrins on the Chemical Stability of ST1435, a Contraceptive Steroid Progestin, in Aqueous Solution

The influence of cyclodextrins (CDs) on the chemical stability of the contraceptive steroid progestin, ST1435, in aqueous solution has been studied using reversed phase high performance liquid chromatography. The effects of CD structure, temperature, and CD concentration on the rate of degradation were investigated. It was found that the drug degraded to different extents following a pseudo-first order reaction mechanism. The presence of the host molecules affected the degradation rate as a result of complexation which might result in protection of the labile moiety of the drug molecule against degradation. Hydroxypropyl--cyclodextrin (HP--CD) and hydroxyethyl--cyclodextrin (HE--CD) retarded the degradation in contrast to -cyclodextrin (-CD) which accelerated the steroid degradation. The stabilizing action of HP--CD is larger than that of HE--CD. The degradation rate increased upon increasing temperature and the Arrhenius equation is valid. Lineweaver-Burk equation analysis indicated that the steroid included inside the CD cavity degraded three times more slowly than did the free ST1435 in solution. This equation further supported the formation of a 1 : 1 inclusion complex between ST1435 and HP--CD with a stability constant of 934.5 M-1 at 65°C.     

Binding of vitamin A byβ-cyclodextrin and heptakis(2,6-O-dimethyl)-β-cyclodextrin

Inclusion complexation of all-trans-retinol, retinal and retinoic acid with -cyclodextrin (-CD) and heptakis(2,6-O-dimethyl)--cyclodextrin (DM--CD) were investigated by means of UV-vis spectroscopy. The association constants (K _a) obtained for vitamin A with DM--CD is greater than with -CD. On the other hand, for the same host compoundK _a values of retinol, retinal and retinoic acid are very close to each other.     

β-Cyclodextrin Mediated Synthesis of Syndiotactic-rich Polystyrene

Stereoregular polystyrene (PS) was prepared using various molarequivalents of -cyclodextrin (-CD) by polymerisingstyrene in the presence of -CD. Stereoregular (isotactic,atactic and syndiotactic) distributions of the preparedpolystyrene polymers were determined from terminal modelBernoullian statistics using ¹³C NMR data. Inclusioncomplexation of styrene by -cyclodextrin was detected byUV-Visible spectroscopy, which gave a binding constant value of31606 ± 3350 M^-1 for the 1 : 1 complex. With anincrease in the styrene : -CD ratios, the proportionof syndiotactic polymers increased. The glass transitiontemperature (T_g) of the polymer also increased along withmelting temperature (T_m) at higher styrene : -CDratios. In addition, the molecular weight of the polymers prepareddecreased with increase in the -CD concentration.     

Silver ion spray reagent for the discrimination of β- and ε-end groups in carotenoids on thin-layer chromatograms

Summary Thin-layer chromatograms of pure carotenoids and natural carotenoid mixtures were dried and sprayed with saturated methanolic silver nitrate solution. Those carotenoids containing -end groups showed a marked bathchromic colour change for each such end group. Thus, -carotene, -cryptoxanthin and zeaxanthin gave a clear red colour while -carotene, -cryptoxanthin and lutein gave deep organge spots after such treatment. Taraxanthin and antheraxanthin could be similarly distinguished. The method was not applicable to paper chromatography.     

Struktur/Geruchs-Beziehungen von mit β-Santalol verwandten Verbindungen:E-Homo-β-santalol undE-Dehydrohomo-β-santalol

Summary To study the structure/odour relationships of -santalol analogues two homologous -santalol derivatives5 and6 were synthesized. The key steps thereby were the -alkylation of the bicyclic starting ketones8 and14 accomplished by using more drastic conditions as usual. The odours of5 and6 are described in detail.

Auszugsweise vorgetragen am 19th International Symposium on Essential Oils and Other Substrates, 9. September 1988, Greifensee/Dübendorf, Schweiz