1,4-bis(4′-hydroxy-1′,2′,5′-trimethyl-4-piperidyl)-1,3-butadiyne and its derivatives

1.4-Bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)-1.3-butadiyne has been synthesized from the individual isomers of 4-ethynyl-1,2,5-trimethyl-4-piperidol. Hydrogenation, bromination, and cleavage have given, respectively, 1,4-bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)butane, 1,4-bis(4-nydroxy-1,2,5-trimethyl-4-piperidyl)-1,2,3,4-tetrabromo-1, 3-butadiene, and 4-(1,3-butadiynyl)-1,2,5-trimethyl-4-piperidol.     

Isoflavones of the roots of Lupinus luteus

Conclusions For the first time in the isoflavone series, a compound which has the structure of 5,7-dihydroxy-3,4-methylenedioxyisoflavone (3,4-methylenedioxyorobol) and two of its glucosides — 3,4-methylenedioxyorobol 7-O--D-glucoside and 3,4-methylenedioxyorobol 7-O--D-glucosylglucoside — and also a genistein C-monoglucoside, have been described. The isoflavones were isolated from the roots ofLupinus luteus L. by preparative chromatography on paper and on columns of polyamide. In addition, the previously known genistein, genistein 7-O--D-glucoside (genistin), and genistein 7-O--D-glucosylglucoside have been obtained.V. F. Kuprevich Institute of Experimental Botany, Academy of Sciences of the Belorussian SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 162–166, March–April, 1974.     

Transformed steroids. 160. Reaction of 20,20-dimethoxy-16α,17α-epoxypregn-5-ene-3β, 21-diol-20-one with pyridine thiocyanate and carbethoxyhydrazine

Conclusion The reaction of 20,20-dimethoxy-16,17-epoxypregn-5-ene-3,21-diol-20-one with pyridine thiocyanate in the presence of carbethoxyhydrazine proceeds by two competing paths: cisopening of the oxide ring by a -SCN ion at the C¹⁷ atom, and substitution of one of the methoxyl groups by -NCS ion. As a result 2,20-dicarbethoxyhydrazones of pregn-5-ene-3,21-diol-20-one-[17,16-d]-1,3-oxathiolan-2-one and 20-methoxy-16,17-epoxypregn-5-ene-3-ol-[20,21-d]-1,3-oxazolidine-2-thione are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 911–914, April, 1987.     

Synthesis of 2,3,7,8-tetramethyldibenzofuran

3,4,3,4-Tetramethyldiphenyl ether readily forms 2,2-dihalo derivatives on bromination and iodination. Heating 2,2-diiodo-4,5,4,5-tetramethyldiphenyl ether with copper powder or oxidation, of 2,2-dilithio-4,5,4,5-tetramethyldiphenyl ether gives 2,3,7,8-tetramethyldibenzofuran, the structure of which was proved by alternative synthesis from 2,2-dinitroand 2,2-diamino-4,5,4,5-tetramethyldiphenyls.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1597–1599, December, 1972.     

Über Inhaltstoffe der Iris germanica (Schwertlilie)

Acetovanillon and the known flavonoids irisolidone, irigenin, irisolone, tectorigenin and dihydroquercetin-7.3-dimethylether were detected in the rhizomes of Iris germanica. Also a few unknown compounds could be isolated and their structure elucidated; 9-methoxy-7-(3.4.5-trimethoxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.3.4.5-tetramethoxy-6.7-methylenedioxyisoflavone (III A); 9-methoxy-7-(3.4-dimethoxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.3.4-trimethoxy-6.7-methylenedioxyisoflavone(III B); 9-hydroxy-7-(p-hydroxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.4-dihydroxy-6.7-methylenedioxyiosoflavone (IX); 5.7-dihydroxy-3-(3-hydroxy-4-methoxyphenyl)-6-methoxy-4H-1-benzopyran-4-on (=5.7.3-trihydroxy-6.4-dimethoxyisoflavone (XI B); 5.7-dihydroxy-3-(4-hydroxy-3-methoxyphenyl)-6-methoxy-4H-1-benzopyran-4-on (=5.7.4-trihydroxy-6.3-dimethoxyisoflavone (XI C).The structure determination was effected by combined spectroscopical and chemical methods.

---

---

Herrn Prof. Dr.F. Hecht mit den besten Wünschen zum 70. Geburtstag gewidmet.     

Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.     

Effects of tempering time and tempering temperature of caustic mercerization on the spectral and electrical properties of Egyptian cotton fibres

Several samples of Egyptian cotton fabric strips were subjected to various caustic mercerization conditions, varying in temperature and time. On these samples extensive measurements were undertaken, comprising X-ray diffraction, IR absorption spectra and the temperature-dependence of DC-electric conductivity.The phase constitution, % crystallinity, IR band assignment, activation energies for conduction and energy gap were evaluated as a function of caustic mercerization. The results obtained were correlated and discussed in detail, leading to valuable information of use in the cotton fabric strip industries.

---

Zusammenfassung Verschiedene Proben von ägyptischen Baumwollstreifen wurden unter verschiedenen Bedingungen (Temperatur, Zeit) einer Laugung unterworfen. Die gelaugten Proben wurden eingehend durch Röntgendiffraktometrie, IR-Absorptionsspektroskopie und Messungen der Temperaturabhängigkeit der elektrischen Gleichstromleitfähigkeit untersucht. Phasenstruktur, Kristallinität, Zuordnung der Banden, Aktivierungsenergien für die Leitfähigkeit und verbotene Bänder wurden in Abhängigkeit von der Laugung ermittelt. Die erhaltenen Ergebnisse wurden miteinander verglichen und in Einzelheiten diskutiert, wobei für die Baumwollverarbeitungsindustrie wertvolle und empfehlenswerte Informationen erhalten wurden.

---

. , . , , , . , .

     

Anomalous nucleosides

A preparative synthesis of the antimetabolite 6-azacytidine is described which involves the amination under mild conditions without the use of an autoclave of 2, 3, 5-tri-O-acyl-4-thip-6-azauridines with the isolation of the intermediate 2, 3, 5-tri-O-acyl-6-azacytidines and subsequent elimination of the protective groups at room temperature.For communication VI, see [10].     

Structure of some components of the roots of Prangos ferulacea

Summary From a methanolic extract of the roots ofPrangos ferulacea (L) Lindl., growing in the Nakhichevan ASSR, in addition to the compounds found previously, another six substances (I–VI) have been isolated, of which (I) and (VI) have been identified as, respectively, meransin hydrate monoacetate, found for the first time in nature, and umbelliferone: and in the study of a crystalline mixture obtained from the resin of the roots of the plant under investigation collected in Armenia, two coumarins — (VII) and (VIII) — have been isolated.On the basis of a study of IR, NMR, and mass spectra and chemical properties, the structures of the six new cumarin derivatives (II–V, VII, and VIII) have been established. Compound (II) has the structure of 8-(3-methylbutenyloxy)furo-2,3:7,6-coumarin and has been called feruliden; (III) is 7-hydroxy-8-(3-hydroxy-2-senecioyloxyisopentyl) coumarin and has been called ferudiol; (IV) is 7-hydroxy-8-(3-methoxy-2-senecioyloxyisopentyl) coumarin; (V) is 5-[1-(2,3-dihydroxy-3-methylbutyroyloxy)-1-methylethyl]-4,5-dihydrofuro-2,3:7,6-coumarin and has been called lindiol; (VII) is 8-(2-hydroxy-3-methylbut-3-enyloxy)-7-methoxycoumarin and has been called ferudenol; (VIII) is 7-methoxy-8-(3-methyl-2-oxobut-3-enyl)coumarin and has been called prangone.Leningrad Sanitary-Hygenic Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 568–574, September–October, 1974.     

1,2-bis(2',6'-dimethyl-i',3'-dioxa-6'-aza-2'-silacyclooctyl-2')ethane and the corresponding ethylene and acetylene derivatives

Conclusions The reaction of 1,2-bis(methyldimethoxysilyl)ethane and the corresponding ethylene and acetylene derivatives with bis(2-hydroxyethyl)methylamine gives 1,2-bis(2,6-dimethyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)ethane and the corresponding ethylene and acetylene derivatives. Analogously, 1,2-bis(vinyldimethoxysilyl)acetylene gave 1,2-bis(2-vinyl-6-methyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)acetylene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1420–1421, June, 1988.     

Coumarins of Seseli tenuisectum

Summary The herbSeseli tenuisectum has been found to contain — in addition to anomalin — another three coumarins (C-2, C-3, and C-4) which are derivatives of khellactone.On the basis of NMR, mass, and IR spectroscopy, the products of stepwise alkaline methanolysis and hydrolysis, and conversion into pteryxin, it has been established that two of them are isomeric monoesters of khellactone and angelic acid with the structures 3-angeloyloxy-4-hydroxy- and 4-angeloyloxy-3-hydroxy-3,4-dihydroxyseselin, respectively. They have been obtained in the individual state for the first time by thin-layer chromatography, which has enabled their IR spectra to be recorded.The lactone C-4 is a diester of khellactone with the structure 4-angeloyloxy-3-isovaleryloxy-3,4-dihydroseselin.We are the first to have found these substances in plants of the flora of the USSR.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 38–43, January–February, 1972.     

Synthesis of 5′-deoxy-5′-[18F]fluoro-adenosine by Radiofluorination of 5′-deoxy-5′-haloadenosine Derivatives

5-Deoxy-5-[¹⁸F]fluoro-adenosine was synthesised by nucleophilic radiofluorination reactions of 5-deoxy-5-haloadenosines. The homogeneous isotope exchange in 5-deoxy-5-fluoro-adenosine was also investigated. The conversion of these reactions was found to be rather low and depends on the strength of the halogen-carbon bond: 0.248% for chloride-, 0.488% for bromide- and 1.070% for iodide-derivative; there was no reaction observed in the case of fluoro-compound.     

Polarographic behavior of 2,2′-bifuryl and 2,2′-furoin

In aqueous and aqueous-ethanolic buffer solutions at pH<9, 2, 2-bifuryl and 2, 2-furoin give two-electron polarographic electroreduction waves, the half-wave potentials of which depend on the pH. The primary product of the electroreduction of 2, 2-bifuryl is trans-1,2-dihydroxy-1,2-bis(, -furyl)ethylene, which then rearranges into 2, 2-furoin. The anode-cathode wave of 2,2-bifuryl has been studied by means of a Kalousek commutator. It has been shown that the polarographic behavior of 2,2-bifuryl and 2, 2-furoin is similar to that of benzil and benzoin, but differs from the behavior of analogs of the pyridine series.     

Spectral and catalytic properties of a chromium-containing polymeric complex

The spectral and catalytic properties of octahedrally coordinated polymeric Cr³⁺ ions are compared with those of the same ions in-Cr₂O₃. A relationship between the character of the nearest ligand environment of the Cr³⁺ ion (according to spectral data) and the catalytic activity was found. The exchange interaction between Cr³⁺ ions of the polymer chain exerts no significant influence on the catalytic activity.

---

Cr³⁺ , Cr³⁺ -Cr₂O₃. Cr³⁺ ( ) . Cr³⁺ .

     

Untersuchung des Zerfalls verschiedener Azoinitiatoren in Lösung

The decomposition of various symmetric and unsymmetric azo-initiators (1,1-dichloro-1,1-diphenyl-1,1-azoethane, 2,2-dichloro-2,2-azopropane, 1,1-dichloro-1,1-azocyclohexane, 2,2-diacetoxy-2,2-azopropane, 1,1-diacetoxy-1,1-diphenyl-1,1-azoethane, 1,1-diacetoxy-1,1-azocyclohexane, 2,2-dipropionoxy-2,2-azopropane, 2,2-dicapronoxy-2,2-azopropane, 4,4-dimethyl-1,4-azobutyrolactone, azoisobutyronitrile, 2-t-butylazo-2-cyanobutan, 2-t-bytylazo-1-cyanocyclohexan) in solution was studied in dependence of temperature. Volumetry and differential-scanning-calorimetry (DSC) were used to determine decomposition rates; first order kinetics was found in all cases.

     

Spirocyclic betaines or 2-amino-Δ2-1,3,4-thiadiazoline-5-acetic acid and their rearrangement in acetic anhydride

Reaction of N-(1-pyrrolidinyl)-, N-(1-piperidinyl)-, N-(4-morpholinyl)-, and N-(1-hexahydroazepinyl)-thioureas with propiolic acid gives hetero-N-spiro-4-(2-amino-²-1,3,4-thiadizolin-4-io-5-acetates), which rearrange in acetic anhydride to 2-(N-heteryl)imino-2,3-dihydro-4H-1,3-thiazin-4-ones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 263–265, February, 1993.     

Solid-gas reactions: Study of sulphation of limestone using thermogravimetry

Comparative data are presented on the absorption rate and capacity for SO₂ capture by a natural Polish limestone with and without sodium chloride additive. Two sets of experiments were carried out, under dry and wet conditions during limestone calcination and sulphation.The presence of water vapour brought about a higher reactivity of the sorbent, probably as a result of an effect on the sintering of lime and through the influence of the CaSO₄ layer. Further morphological investigations could provide confirmation of the present hypothesis.

---

Zusammenfassung Absorptionsgeschwindigkeit und -kapazität für SO₂ an einem polnischen Kalkstein mit oder ohne NaCl-Zusatz werden verglichen. Zwei Reihen von Experimenten wurden in trockener bzw. wasserdampfhaltiger Atmosphäre bei der Calcination und Sulfatbildung durchgeführt. In Gegenwart von Wasserdampf wird die Reaktivität des Absorbens infolge Sinterung des Kalks und trotz des Einflusses der CaSO₄-Schicht erhöht. Künftige morphologische Untersuchungen sollen diese Hypothese eventuel bestätigen.

---

. . , , . .

---

---

The author would like to thank Prof. E. M. Bulewicz of this Institute for valuable discussions, and Mr. W. Balcerowiak for making available the facilities of the Laboratory of the Institute of Heavy Organic Synthesis in Kdzierzyn-Kole.     

Transformed steroids. 190. Influence of Co-complexation on the epoxide ring opening of 17β-ethynyl-16α,17α-epoxyandrost-4-en-3-one on reacting with pyridine hydrofluoride,pyridine hydrochloride,and pyridine thiocyanate

The epoxide ring opening of 16,17-epoxy-17-ethynylandrost-4-en-3-one and its dicobalt hexacarbonyl complex on reacting with Py·HF, Py·HCl, and Py·HSCN was studied. The results of these reactions and the structure of the end products depend not only on the complexation of the acetylene bond, but also on the nucleophilic reagent used. On the basis of the reaction of a Co-coordinated 16,17-epoxy-17-ethynylandrost-4-en-3-one there has been developed a preparative method for the synthesis of pregn-4-ene-3,20-dione-[17,16-d]-1,3-oxazolidin-2-one.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2661–2666, November, 1992.     

Preparation and stereochemical characterization of some N-acyl-[1]benzopyrano[3,4-c]pyrazole derivatives from rotenoids

Summary Several new N-acyl derivatives of 1-(4-hydroxy-2,3-dihydrobenzofuran-5-yl)-7,8-di methoxy-1,9 b,2,3,3 a,4-hexahydro-[1]benzopyrano[3,4-c]pyrazole-1-ene have been prepared by appropriate chemical transformation of isohydrazones of rotenone and amorphigenin. A study of their¹H- and¹³C-NMR spectra confirmed the presence of the twocis 3a, 9b, 2 and 3a, 9b, 2 diastereomers in the parent isohydrazones and revealed the strong predominance of the conformers withendo orientation of the 3-NAc group. The conformations due to rotation about the 1,5-bond between rings C and D in the 4-OH and 4-O-substituted compounds were also determined by taking into account the anisotropic effect of aromatic rings A and D, and the hydrogen bond between 4-OH and the 2-N atom, as well as by inspecting the Dreiding models.

---

Darstellung und stereochemische Charakterisierung einiger N-Acyl-[1]benzopyrano[3,4-c]pyrazol-Derivate von Rotenoiden

Zusammenfassung Mittels geeigneter chemischer Transformationen von Isohydrazonen von Rotenon und Amorphigenin wurden einige neue N-Acyl-Derivate von 1-(4-Hydroxy-2,3-dihydrobenzofuran-5-yl)-7,8-dimethoxy-1,9 b,2,3,3 a,4-hexahydro-[1]benzopyrano[3,4-c]pyrazol-1-en hergestellt. Eine Untersuchung ihrer¹H und¹³C-NMR-Spektren zeigt die Gegenwart von zweicis 3a, 9b, 2- und 3a, 9b, 2-Diastereomeren in den Ausgangs-Isohydrazonen und eine starke Bevorzugung der Konformeren mitendo-Orientierung der 3-NAc-Gruppe. Die Konformationen bezüglich der Rotation um die 1,5-Bindung zwischen Ring C und D werden für die 4-OH und 4-O-substituierten Verbindungen unter Berücksichtigung von Anisotropie-Effekten der aromatischen A- und D-Ringe, der Wasserstoffbrücken zwischen 4-OH und dem 2-N Atom und auch der Betrachtung der entspechenden Dreiding-Modelle diskutiert.