Rearrangement ofα -trifluoromethyl-β-dialkylamino-β-fluoroacrylic acid N.N-dialkylamides

Conclusions When heated in the presence of a catalytic amount of BF₃ etherate,-trifluoromethyl--diethylamino--fluoroacrylic acid N, N-dimethylamide is reversibly isomerized to-trifluoromethyl--dimethylamino--fluoroacrylic acid N, N-diethylamide. The methyl esters of-trifluoromethyl--diethylammo--fluoroacrylic acid and-trifluoromethyl--phenoxy--fluoroacrylic acid N,N-dimethylamide are not isomerized under the same conditions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No.1, pp.137–141, January, 1976.     

Steroid compounds of marine sponges. VII. Preparation of derivatives of sokotrasterol and halistanol sulfates and structure-activity interrelationships among these compounds

Five new sulfated derivatives of sokotrasterol and halistanol have been obtained: 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate); 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate) 23-palmitate; 24,25-dimethyl-5-cholestane-2,3,6-triol 3-(sodium sulfate); 24,25-dimethyl-5-cholestane-2,3,6-triol 6-(sodium sulfate); and 24,25-dimethyl-5-cholestane-2,3,6-triol 2,6-di(sodium sulfate). The inhibiting and membranolytic properties of the polysulfated steroids from sponges and their derivatives have been studied. It has been shown that physiological activity in this series of compounds depends on biphilicity.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 441–445, July–August, 1986.     

Radiation-induced reactions of cholesterol in an aqueous medium

⁶⁰Co -ray radiolysis of cholesterol /3-hydroxy-5-cholestene/ /I/ in the two-phase system /water-ethyl acetate/ and in the presence of air has been studied using TLC and GC methods. The following products were observed in the irradiated mixture: 3, 7-dihydroxy-5-cholestene /II/, G O. 36, 3-hydroxy-7-keto-5-cholestene /III/, G 1.48, 3-hydroxy-7-keto-5-cholestane /IV/, G 0.22, 3,5,6-trihydroxy-5-cholestane /V/, G 0.83, 5,6-epoxy-3-hydroxy-5-cholestane /VIa/, G 0.26, 5,6-epoxy-3-hydroxy-5-cholestane /VIb/, G 0.24, and 2, 3-dihydroxy-5-cholestene /VII/, G 0.22. The dose dependence of the formation of these products shows that the cholesterol derivatives substituted in the position 7 /II–IV/ are formed from a common precursor — the radical Ia. On the other hand, the products of the 5–C=C double bond reactions /V and VI/ are formed independently. Also the product VII is formed independently. A reaction scheme that is in agreement with these results is proposed.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

α-Iodo-β-nitrostilbene in the reaction with morpholine and piperidine

The reaction of -iodo--nitrostilbene with morpholine or piperidine yields -nitro--morpholino- or -nitro--piperidinostilbene. The reaction is regioselective and stereospecific: only the iodine, and not the nitro group, is substituted; the product obtained has acis structure regardless of whether the initial substrate had acis- or atrans-configuration. The prereaction stage probably includes the formation of a charge-transfer complex between substrate and reagent.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1214–1216, May, 1992.     

Polymorphism of (+)N-tosyl-L-glutamic acid

It has been shown that polymorphism is the reason for the occurrence of (+)N-tosyl-L-glutamic acid 1 with various melting points. 1 occurs in two crystalline forms: and . Form -1 (prisms) having a melting point of 145–147°C is chemically pure and stable. Form -1, however, is unstable and is formed as a result of the stabilizing effect of an organic solvent not introduced into the structure of the crystal. At about 125°C the forms is transformed to the form. The melting point of the form depends on the amount and type of solvent contained in the crystal, which, during measurement cannot leave the system.     

Culcitosides C2 and C3 from the starfishCulcita novaeguineae

Two steroid glycosides not previously described have been isolated from the digestive system of the starfishCulcite novaeguiniae, and these have been called culcitosides C₂ and C₃. With the aid of chemical and spectral methods, the chemical structure of C₂ has been established as 24-methyl-5-cholestane-3,4,6,8,15,16,28-heptaol 28-O-[O-(2,4-di-O-methyl--D-xylopyranosyl)-(1 2)--L-arabinofuranoside, and that of C₃ as its 4-deoxy analogue.Pacific Ocean Institute of Bioorganic Chemistry of the Far Eastern Scientific Center of the USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 592–596, September–October, 1986.     

Thermal decomposition of phosphorylated hemimercaptals

Conclusions The reaction of diphenylchlorophosphine with ,,-trichloro--hydroxyethyl ethyl sulfide in the presence of triethylamine leads to the formation of -ethylthio-,,-trichloroethyl diphenylphosphonite. The reaction of diphenylchlorophosphine with dimethyl -hydroxy--propylthiophosphonate in the presence of triethylamine gives -propylthio--dimethylphosphonoethyl diphenylphosphonite. The phosphorylated hemimercaptals obtained are thermally unstable and decompose to S-alkyl diphenylthiophosphonites and the corresponding carbonyl compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2619–2621, November, 1985.     

Steroids

Summary 1. A new type of steroido[17, 16-d]-3-(methyl, phenyl)isoxazoles has been synthesized by the cyclization of the syn-oximes of acylated 3-hydroxy-16, 17-oxidopregn-5-en-20-ones or their 5-saturated derivatives and acylated 17-benzoyl-3-hydroxy-16, 17-oxidoandrost-5-ones.2. It has been established that the Beckmann rearrangement of the anti-oximes of acylated 17-benzoyl-3-hydroxy-16, 17-androst-5-enes leads to a mixture of anilides and steroidoisoxazoles, which shows the inversion of the configuration of the oximes (from the anti to the syn form) during the rearrangement.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 5, pp. 325–333, 1966     

Reaktion der Azlactone mit Aminoverbindungen, 3. Mitt.: Über die Herstellung der Phenylhydrazide und 4-Nitrophenylhydrazide einiger α,β-disubstituierter Acrylsäuren

Zusammenfassung Ungesättigte Azlactone spalten sich mit Phenylhydrazin bzw. 4-Nitro-phenylhydrazin auf unter Bildung der Phenylhydrazide (1a–1o) bzw. 4-Nitro-phenylhydrazide (2a, 2b) der entsprechenden ,-disubstituierten Acrylsäuren. Zum Unterschied von den durch die Hydrazinolyse entstandenen Hydraziden der ,-disubstituierten Acrylsäuren, die sich leicht zu 3,5-disubstituierten 6-Hydroxy-1,2,4-triazinen^{1, 2} bzw. zu Pyrazolderivaten^{3, 4, 5} cyclisieren lassen, ist es nicht gelungen, unter gleichen Bedingungen die Phenylhydrazide bzw. 4-Nitro-phenylhydrazide zu cyclisieren. Zum Strukturbeweis dienten NMR-Spektren.

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Reaction of azlactones with amino compounds, III: Preparation of the phenylhydrazides and 4-nitrophenylhydrazides of several ,-disubstituted acrylic acids

The reaction of phenylhydrazine and 4-nitrophenylhydrazine with several unsaturated azlactones has resulted in their cleavage to the phenylhydrazides (1a–1o) and 4-nitrophenylhydrazides (2a, 2b), respectively, of the corresponding ,-unsaturated acrylic acids. In contradistinction to the hydrazides of ,-unsaturated acrylic acids, which had previoulsy been obtained by hydrazinolysis of unsaturated azlactones and had easily undergone cyclisation to 3,5-disubstituted 6-hydroxy-1,2,4-triazines^{1, 2} or pyrazole derivatives^3–5, the phenylhydrazides and 4-nitrophenylhydrazides could not be cyclised under comparable conditions. NMR spectroscopy was used to ascertain the structures of the reaction products.

     

Approaches to the synthesis of pregn-5-en-3β,21-diol-20-one-[16,17α-d]-2'-methyloxazoline

Conclusions Two independent methods were found for the preparation of pregn-5-en-3,21-diol-[16,-17-d]-2'-methyloxazoline: 1) by cis-opening of the aziridine ring of the 3;16,17;21-triacetate of 16,17-epiminopregn-5-en-3,21-diol-20-one and 2) by the 21-hydroxylation of pregn-5-en-3-o1-20-one-[16,17-d]-2'-methyloxazoline using iodosobenzoyl diacetate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2138–2141, September, 1984.     

Mass spectrometric study of monoalkyl-substituted thiacyclanes

Monosubstituted - and -alkylthiophans and -, -, and -alkylthiacyclohexanes were subjected to a comparative mass spectrometric study. The stability of the M⁺ ion increases on passing from - to -alkylthiophans and from - to - and -alkylthiacyclohexanes. In the case of -alkylthiophans and - and -alkylthia-cyclohexanes the principal process is associated with ejection of the substituent as a whole, whereas a portion of the alkyl substituent, with retention of one CH₂ group in the composition of the charged fragment, is eliminated from the molecular ions of -alkylthiophans and -alkylthiacyclohexanes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 176–181, February, 1978.     

Researches on imidazoles

A study is made of the reaction of the sodium and ammonium salts of 1 -alkyl- and 1, 2-dialkyl-4-nitro-5 mercaptoimidazoles with -halogenoketones, -halogenoalcohols, and — and -halogeno acids, to give a number of 1 -alkyl- and 1, 2-dialkyl-4-nitro-5- [-ketoalkyl (aralkyl)-, -hydroxyethyl-, and -and -carboxyalkyl] mercaptoimidazoles.For Part XXIV see [6].     

Excess enthalpies of aqueous solutions of small peptides at 25°C

Heats of dilution of aqueous solutions of the following di-and tripeptides were determined at 25°C over a wide concentration range: -alanyl-glycine, -alanyl--alanine, DL--alanyl-glycine, glycyl-DL--alanine, L--alanyl-L-alanine, DL--alanyl-DL--alanine, DL--alanyl-DL-valine, DL--alanyl--alanine, glycyl--aminobutyric acid, glycyl-L-leucine and DL--alanyl-glycylglycine. The excess enthalpies H^ex and partial molar relative enthalpies L₂ were calculated and enthalpy coefficients of intermolecular interaction were analysed using the additivity principle of Savage and Wood. The concentration dependence of the enthalpic characteristics of peptide-peptide interactions is discussed based on of their hydrophobicity and hydrophilicity. The three-stage model of peptide association is described using enthalpic coefficients of intermolecular interactions.     

Cardenolides of the seeds ofCoronilla glauca and ofC. scorpioides. New glycosides alloglaucoside and scorpiosidol

Two new glycosides have been isolated from the seeds ofCoronilla glauca L. and C. scorpioides Koch: 3-(0-D-glucopyranosyloxy)-14. 15-dihydroxy-19-oxo-5-card-20(22)-enolide (alloglaucoside) and 3-(-D-gluco-ucofuranosyloxy)-5,14,19-trihydroxy-5-card-20(22)-enolide (scorpiosidol), together with a glycoside previously unknown for theCoronilla genus — 3-(-D-glucopyranosylo)g)-14-hydroxy-5-card-20(22)-enolide (desglucouzarin) and known aglycons (corotoxigenin, alloglaucotoxigenin, coroglaucigenin) and glycosides (glucocorotoxigenin, coronillobioside, glucocoroglaucigenin, coronillobiosidol and scorpioside).Ukraine Pharmaceutical Academy, Kharkov–2. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 372–376, May–June, 1996. Original article submitted August 14, 1995.     

Triterpene glycosides from Pulsatilla chinensis

Four triterpene glycosides were isolated from the roots of Pulsatilla chinensis (Bunge) Regel (Ranunculaceae). Two new glycosides, chinensiosides A (1a) and B (2), were identified as 3-O-[-L-rhamnopyranosyl-(12)--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid and 3-O-{-L-rhamnopyranosyl-(12)-[-D-glucopyranosyl-(14)]--L-arabinopyranosyl}-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid. The other two glycosides were identified as previously known hederasaponin C (3) from Hedera helix and glycoside III (4) from Pulsatilla cernua.     

Ring opening of fluoroalkyl-containing α,β-epoxyketones by aromatic amines

Aromatic amines cause ,-epoxyketones containing a -fluoroalkyl group to undergo ring opening at the -position to give -amino--hydroxyketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 882–883, May, 1994.     

Transformations of solasodine

Solasodine (I) has been subjected to a number of transformations. The following compounds have been obtained from it by described procedures: 3-acetoxypregna-5,16-dien-20-one (II), 3-acetoxypregn-5-en-20-ol (III), and 3-acetoxypregn-5-en-20-ol (IV). The oxidation of (III) and (IV), the formation of an oxime, and the reduction of the oxime with sodium in ethanol, followed by Hess methylation, has led to 20-dimethylaminopregn-5-en-3-ol (IX) and to 20-dimethylaminopregn-5-en-3-ol (X). From compounds (IX) and (X), by analogy with (III) and (IV) by their oxidation and the preparation of oximes, which were then reduced and methylated, the following were obtained: 3,20-bisdimethylaminopregnane (XVII) and 3,20-bisdimethylaminopregnane (XVIII), and also quaternary salts of the latter.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 370–374, May–June, 1980.     

Synthesis of 4,5-Seco-Derivatives of Allobetulin

4,5-Seco-19,28-epoxy-18-olean-3,5-dione wasprepared by ozonation of 19,28-epoxy-18-olean-3(5)-ene. The structures of the synthesized compounds were confirmed using spectral data.