The structure of 16, 17β-epoxy-17α-pregn-5-en-3β-ol-20-one monohydrate

The structure of the title compound (1) has been studied by means of X-ray diffraction. The region of cycleD in epoxide1 was compared with that of the 16,17-epoxy derivatives of progesterone and pregnenolone (studied previously) as well as with that of the respective 16,17- and 16,17-cyclopropano analogs. In contrast to the 16,17-epoxy-20-oxo derivatives, in compound1 the electron conjugation of the epoxide ring with the CH₃CO group at C(17) is partly disrupted. Moreover, the steric congestion at C(17) is significantly less pronounced in 16,17-epoxide1 than in its 16,17-counterpart. Both of these factors, especially steric decongestion, are favorable for nucleophilic attack at C(17) in the molecule of1. The X-ray diffraction data do not contradict the previously advanced mechanism of epoxide ring opening in 16,17- and 16,17-epoxy-20-oxo steroids by nucleophilic reagents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 401–405, February, 1993.     

Zum Verhalten von Ketenen gegenüber P−N-Yliden Reaktionen mit phosphororganischen verbindungen, 39. Mitt.

1,3-Skeletal rearrangement of N-substituted ketimines via a possible intimate ion pair is discussed. (CH₃)₃SiCH=C=O (1) reacts with N-(aziridinyl)-triphenylphosphinimine (2) to give N-(1-aziridinyl)-2-trimethylsilylketen-1-imines (3). The compounds3 b, c are thermally labile and do not undergo 1,3-rearrangement but a retro-ene type reaction to yield (CH₃)₃SiCH₂CN and 2,3-diphenyl-2H-azirine (4). Diphenylketene (5) reacts with N-(N, N-dialkylamino)-triphenylphosphinimines (6) to yield -(N-disubstituted-amino)-nitriles (7). , -Dimethyl--(triphenylphosphinimino)-acetonitrile (9) reacts with (5) at room temperature to form , -dimethyl--(2, 2-diphenylketen-1-imino)-acetonitrile (10) which rearranges at 80° to dimethyl diphenylsuccinonitrile (11). The reaction of5 with 7-(triphenylphosphinimino)-7-azabicyclo[4.1.0]heptane (12) gives tetraphenylsuccinonitrile13 and 7-(7-azabicyclo[4.1.0]heptane)-, -diphenylacetonitrile (14). Finally the synthesis of N-acylketenimines (16) from (5) and acyltriphenylphosphinimines (15) is reported.

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38. Mitt.:Chr. Ivancsics undE. Zbiral, Mh. Chem.106, 839 (1975).     

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.     

Über die Synthese von N,N′-disubstituierten α-Iminophenyl-glyoxylsäurethionamiden und deren Reduktion mit Schwefelwasserstoff zu Phenylessigsäurethionamiden

Zusammenfassung Durch Umsetzung von ,-Dichloracetophenon mit überschüss. prim. Amin und Schwefel in äther. Lösung unter Zusatz von K₂CO₃ (Reaktionszeit 140 Stdn., Reaktionstemp. max. 20°) können N,N-disubstituierte -Iminophenylglyoxylsäurethionamide (1–3) in guten Ausbeuten synthetisiert werden.-Iminoglyoxylsäurethionamide (4–6), die am Imin- bzw. Aminstickstoff auch unterschiedlich substituiert sein können (4, 6), erhält man aus den entsprechenden Phenylglyoxylsäurethionamiden durch Umsetzung mit überschüss. primären Aminen.Die -Iminophenylglyoxylsäurethionamide können bereits bei Raumtemp. glatt durch H₂S zu den entsprechenden Phenylessigsäurethionamiden reduziert werden.

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Synthesis of N,N-disubstituted -iminophenyl-thioglyoxylic amides, and their reduction by means of H₂S to phenyl-thioacetic amides (Willgerodt—Kindler reaction, V.)

N,N-Disubstituted -iminophenylthioglyoxylamides (1–3) can be synthesized in good yields by the reaction of ,-dichloroacetophenone with excess primary amine and sulphur in eth. solution in the presence of potassium carbonate (reaction period 140 hours, reaction temperature max. 20°C).-Iminothioglyoxylamides (4–6), which may be differently substituted at the imine and amine nitrogen atoms (4, 6), may be obtained from the corresponding phenylthioglyoxylamides by reaction with an excess of primary amines.The -iminophenylthioglyoxylamides can be reduced smoothly at room temperature by hydrogen sulphide to the corresponding phenylthioacetamides.

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4. Mitt.:F. Asinger, A. Saus undA. Mayer, Mh. Chem.98, 825 (1967).

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Vgl. auchF. Asinger undH. Offermanns, Angew. Chem.79, 953 (1967).     

Polyhydroxysteroids from the Far-Eastern starfishCtenodiscus crispatus

Four new polyhydroxysteroids, 5-cholesta-3,5,6,15,16,25,26-heptaol, 24-ethyl-5-cholesta-3,5,6,15,28,29-heptaol-29-sulfate, (22E)-24-methyl-5-cholest-22-ene-3,5,6,15,25,26-hexaol-26-sulfate, 24-propyl-5-cholesta-3,5,6,8,15,28,29-heptaol, and the known 5-cholesta-3,5,6,15,16,26-hexaol, have been isolated from the starfishCtenodiscus crispatus.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1821–1825, October, 1994.     

Deutung der K α-satelliten bei leichten Elementen

Zusammenfassung Ausgehend von der KL-Ionisation wurden die K -Satelliten(, , ₃, ₃, ₄) der Elemente Z=8 bis Z=12 den entsprechenden Übergängen zugeordnet. Die Berechnung der Übergänge wurde nach der Z-Dependence-Theorie bis einschließlich zweiter Näherung durchgeführt.

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Interpretation of the K -satellites of the light elements

Starting from the KL-ionisation the K -satellites(, , ₃, ₃, ₄) of the elements Z=8 to Z=12 have been assigned to the corresponding transitions. The transitions have been calculated by the Z-dependence-theory including the second approximation.

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Résumé Les satellites K (, , ₃,₃, ₄) des éléments Z= 8 à Z=12 ont été attribués aux transitions correspondantes à partir de l'ionisation KL. Les transitions ont été calculées par la théorie dépendant de Z en tenant compte de l'approximation seconde.

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Herrn Prof. Timm in dankbarer Würdigung der Hilfen, die die BASF für den Aufbau unserer theoretisch-chemischen Arbeitsgruppe geleistet hat, zum 60. Geburtstag gewidmet.

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Der Deutschen Forschungsgemeinschaft dankt D. H. für die finanzielle Unterstützung, die die Dunchführung dieser Arbeit wesentlich erleichterte.     

Possibilities of applying the piloyan method of determination of decomposition activation energies in the differential thermal analysis of polynitroaromatic compounds and their derivatives

Piloyan activation energiesE as well as initals of exothermT _D of sevenN-monoalkyl and fiveN,N-dialkyl-2,4-dinitroanilines were determined. Relationships were found between the T_D values and R_f factors as well asE values and those R_M functions and also theET _D ^–1 term and R_M functions.

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Zusammenfassung Die AktivierungsenergienE nach Piloyan sowie die Anfangswerte der ExothermenT _D wurden für siebenN-Monoalkyl- und fünfN,N-Dialkyl-2,4-dinitroaniline bestimmt. Die Zusammenhänge zwischen denT _D-Werten und den papierchromatographischenR _f-Faktoren der gemessenen Dinitroaniline wurden abgeleitet und erörtert. Desgleichen wurden auch die Zusammenhänge zwischen denE-Werten und denR _M-Funktionen der Papierchromatographie abgeleitet und erörtert. Auch zwischen dem AusdruckE ·T _D ^–1 und denR _M-Funktionen wurde ein Zusammenhang gefunden.

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Résumé On a déterminé les températures initialesT _D de l'effet exothermique ainsi que les énergies d'activationE d'après la méthode de Piloyan, de sept N-mono alcoyl et cinqN,N-dialcoyl-2, 4-dinitroanilines. Une corrélation entre les valeursT _D et les facteursR _f de la Chromatographie sur papier des dinitroanilines étudiées a été trouvée et discutée, ainsi qu'entre les valeursE et les fonctionsR _M de la Chromatographie sur papier. Une relation entre le termeE ·T _D ^–1 et les fonctionsR _M a également été trouvée.

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E T _D N- N,N- -2,4- . _D R _f , E R _M. E. _D ^–1 R _M.

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The authors would like to thank Mrs. Anna Collàkovà for careful DTA measurements, and Dr. Ladislav Smolka for help in treatment of the measured results with the Wang 600 computer.     

Extraction of Polonium from Aqueous α-Hydroxyisobutyric Acid Solutions Using Dioctyl Sulphide, Cyanex 272, Cyanex 301 or Cyanex 302 in Toluene

A study of the extraction of polonium from aqueous solutions containing -hydroxyisobutyric acid (-HIBA) was performed with four different extractants, di-n-octyl sulphide (DOS), Cyanex 272, Cyanex 301 and Cyanex 302, dissolved in toluene. The extracted complex for DOS at low -HIBA concentrations is most likely PoO(-HIB)₂·2DOS, while at higher -HIBA concentrations there seems to be a solvating effect implicating an extracted complex of the type PoO(-HIB)₂(-HIBA)₂·2DOS. For the extraction of polonium with Cyanex 272 the results are inconclusive. The extracted complex is either PoOA₂ or PoO(-HIB)₂·2HA. For extraction with Cyanex 301 or Cyanex 302 the major extracted species does not contain any -HIBA molecules. The neutral species in both cases is PoOA₂, extracted at low extractant concentrations, while at higher extractant concentrations a complex of the type PoOA₂·xHA is extracted. The extraction of polonium increases in the order Cyanex 272 < DOS < Cyanex 302 < Cyanex 301.     

Dynamic shear modulus in the splitting region of poly(alkyl methacrylates)

A systematic study of the dynamic shear modulusG ^*=G+G in three poly(alkyl methacrylates) (PEMA, PnPMA, PnBMA) at frequencies between 0.001 and 500 rad/s is presented. As the splitting frequencies _s are low, aging effects can be observed in the splitting region. There is a systematic shift of the splitting frequency _s to lower values with increasing length of the alkyl side group. In PnBMA a separate shear appearance is observed about two frequency decades below the local mode . This is discussed in terms of the concept of minimal cooperativity. Aging effects are: Shift of the maximum loss frequency to lower values, peak sharpening of the relaxation, and intensity changes of and . These effects are discussed in terms of the sequential aging concept. Aging leads to a pronounced bending of the traces upwards from the equilibrium line in the Arrhenius diagram. These non-equilibrium phenomena are promoted by the small slope m=d(log )/dT of the trace in the splitting region.Dedicated to Prof. E. W. Fischer at the occasion of his 65th Birthday Lieber Herr Fischer, die Hallenser Polymerphysiker danken Ihnen aufrichtig für die warmherzige und effektive Förderung der Polymerwissenschaften im Raum Halle-Merseburg.     

Triterpene Glycosides of Fatsia japonica. IV. Structure of Glycosides D1 and D2 from Seeds

Seeds ofFatsia japonica(Araliaceae) afforded the known hederagenin 3-O--D-glucopyranosyl-(12)-O--L-arabinopyranoside and the new triterpene glycoside D ₂ , for which the structure hederagenin 3-O--D- galactopyranosyl-(12)-O--L-arabinopyranoside was proposed based on chemical methods and NMR spectroscopy     

Energy shift of vanadium Kα X-rays accompanying EC decay in51Cr-labeled compounds

The VK X-rays induced by the electron capture decay of⁵¹Cr-labeled compounds and the fluorescent X-rays of the vanadium compounds have been measured with a Bragg spectrometer. The evident chemical shifts of the K₁ and K₂ lines were observed for the oxidation state both by electron capture and photoionization. The differences of the K peak energy (K₁ and K₂ peaks) with the modes of the excitation were also obtained. The K peaks of⁵¹Cr shift to lower energy by ca. 0.5 eV than those of vanadium at the same oxidation state. This is because the probability of the electron shake up (and shake off) during the electron capture decay is extremely small, as compared to photoionization.     

Analogs of pyrimidine nucleosides

N₁-(-Tetrahydrofuranyl)- and N₁-(-tetrahydropyranyl)uracils and the corresponding 6-azauracils have been obtained by the condensation of bistrimethylsilyl derivatives of uracils and 6-azauracils with-chlorotetrahydrofuran and-chlorotetrahydropyran. The superiority of the silyl method over the mercury method used previously has been demonstrated.For part III, see [9].     

Biosynthesis of asterosaponins from cholesterol and other sterols under the conditions ofin vitro homogenates of starfish gonads and pyloric ceca

Conditions have been selected for performing thein vitro biosynthesis of asterosaponins from cholesterol and other sterols in homogenates and cultures of the gonads and pyloric ceca of Far Eastern starfish. It has been shown that the aglycone moiety of an asterosaponin can be biosynthesized from cholesterol, cholesterol sulfate, 5-cholestanol, and 3,6-dihydroxy-5-cholestane but not from 3, 6-dihydroxy-5-cholestane. Of the give precursors studied, cholesterol was transformed into asterosaponins most completely.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 663–667, September–October, 1985.     

The supramolecular structures and reactivities of some complexes of chiral crown ethers with borane ammonia

Whereas 1 1 crystalline complexes have been isolated between borane ammonia and methyl 4,6-O-benzylidene-2,3-dideoxy--d-galactopyranosido [2,3-b]-1,4,7,10,13,16-hexaoxacyclo-octadecane (1), methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-b] (methyl 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido [2,3-k]-1,4,7,10,13,16-hexaoxacyclo-octadecane (3), and (1R,2R,7R,24R)-3,5,8,11,14,17,20,23,26,28-decaoxatricyclo-[21.4.0.0^2,7]octacosane (4), the hosts, methyl, 4,6-O-benzylidene-2,3-dideoxy--d-mannopyranosido[2,3-b] 1,4,7,10,13,16-hexaoxacyclo-octadecane (2) and 1,4 1,4 3,6 3,6-tetra-anhydro-2,2 5,5-bis-O-oxydiethylenedi-d-mannitol (5) have yielded 2 1 (guest:host) crystalline complexes with borane ammonia as guest. X-ray analyses of the supramolecular structures of BH₃NH₃ ·1, (BH₃NH₃)₂ ·2, BH₃NH₃ ·3, BH₃NH₃ ·4, and (BH₃NH₃)₂ ·5 have been carried out and BH₃NH₃ ·1, BH₃NH₃ ·2, and (BH₃NH₃)₂ ·5 have been shown to reduce acetophenone with enantiomeric excesses of 5, 13, and 10% respectively. Supplementary Data relating to this article (atomic coordinates of the hydrogen atoms and thermal parameters) are deposited with the British Library as Supplementary Publication No. SUP 82017 (74 pages).Dedicated to Professor H. M. Powell.     

Study of gelation using differential scanning calorimetry (DSC)

A new method for determining the degree of conversion of gelation (_gel) and gel time (t _gel) at gel point using a single technology, DSC, is discussed in this work. Four kinds of thermoset resins are evaluated. It is found that the mutation points of reduced reaction rate (V _r ) vs. reaction conversion () curves, corresponding with the changes of reaction mechanism, represents the gelation of the reaction. The at the mutation point is defined as _gel. From isothermal DSC curves, the point at _gel is defined ast _gel. Traditional techniques (ASTM D3532 and DSC method) are also used to determine _gel andt _gel in order to demonstrate this new method. We have found that the results obtained from this new method are very consistent with the results obtained from traditional methods.     

Indole derivatives

A series of -, -substituted -(3-indolyl) ketones was obtained by the reaction of indole with , -unsaturated ketones in the presence of perchloric acid.     

Thermal Investigation of 1,2-propanediamine complexes of nickel(II) in the solid phase

Thermal studies have been carried out on [NiL₃]X₂·n H₂O, whereL=1,2-propanediamine;X=Cl^–, Br^–, SCN^–, 1/2SO ₄ ^2– and 1/2 SeO ₄ ^2– ; andn= 2, 1.5 and 0. [Ni₂L₅(NCS)₂](SCN)₂ and [NiL₂SO₄] have been synthesized pyrolytically in the solid-state from their mother diamine complexes. The deaquation behaviour of [NiL₃]SO₄·2 H₂O appears interesting, and its monohydrate undergoes a solid-state reaction (88–102°) without mass loss, showing an exothermic peak at 95 °C (H=– 5.1 kJ mole^–1).

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Zusammenfassung Thermische Untersuchungen wurden an [NiL₃]X₂,n H₂O ausgeführt, wobeiL-1,2-Propandiamin;X=Cl^–, Br^–, SCN^–, 1/2 SO ₄ ^2– und 1/2 SeO ₄ ^2– ;n=2, 1.5 und 0. [Ni₂Ls(NCS)₂](SCN)₂ und [NiL₂SO₄] wurden ausgehend von den entsprechenden Diaminkomplexen pyrolytisch im festen Zustand synthetisiert. Das Dehydratisierungsverhalten von [NiL₃]SO₄·2 H₂O scheint interessant zu sein, und beim entsprechenden Monohydrat wird eine ohne Massenverlust verlaufende Festkörperreaktion (88–102°) beobachtet, die sich durch einen exothermen Peak bei 95 °C (H=– 5.1 kJ mol^–1) zu erkennen gibt.

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[N³L₃]₂· n₂O, L=1,2-,=l^–, Br^–, SCN^–, 1/2 SO ₄ ^2- , 1/2SeO ₄ ^2- , an=2, 1.5 0. [Ni₂L₅(NCS)₂](SCN)₂ [NiL₂SO₄] . [N³L₃]S₄·2 ₂ , 88–102° , 95 ° =– 5.1 ·^–1.

     

Transformed steroids. 121. Synthesis of the δ-lactone of 3β-acetoxy-16α-hydroxy-6-oxo-24-nor-5α-chol-17(20)-en-23-oic acid

The synthesis of the ¹⁷⁽²⁰⁾-16 analog of natural chiogralactone is described. Attempts to introduce a 6-oxo group directly into the -lactone proved unsuccessful, since the first stage — saponification — took place with the formation of three products: the 3-hydroxy--lactone, the 3-hydroxy-²⁰⁽²²⁾-lactone, and the 15,17(20)-dienoic acid. The synthesis of the desired compound was effected from the ethyl ester of the 5,16-dienoic acid by the scheme 3-acetate3-tosylate6-hydroxy-3,5-cyclosteroid6-oxo-3,5-cyclosteroid6-oxo-5H--lactone. It has been shown that the cyclopropane ring in the 3,5-cyclosteroid -lactone is extremely stable under the conditions of acid treatments.N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 184–187, March–April, 1981.     

Unusual transformation of trimethylsilyloxyisoxazolidines initiated by the fluoride ion

It was found that opening of the isoxazolidine ring of 6a-isopropenyl-1/-trimethylsilyloxy-3, 3a,4,5,6,6a-hexahydro-(1H)-cyclopent[c]isoxazoles by the F^– ion initially gives an intermediate, a tertiary nitrosocompound detected by UV and NMR spectroscopy. Its transformation, finally, into ,-unsaturated aldoximes probably involves an unprecedented allylic migration of the nitroso group.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 461–464, March, 1994.     

Complex polarizability as used to analyze dielectric relaxation measurements

The effect of representing dielectric properties in terms of the complex polarizability ^c = – i is examined. Loss curves ( and tan ) are shifted towards higher frequencies, revealing the existence of new relaxations and allowing the clarifications of ones already known. We have calculated the shift ratios (at maximum or tan )/ (at maximum or tan ) from the more conventional empirical equations representing the dielectric behavior. Some examples are given.