Synthesis of α, α, ω-trihydropolyfluoroalkyl chlorophosphates by the reaction between α,α,ω-trihydropolyfluoroalkyl phosphites and sulfuryl chloride

Conclusions An efficient method for the synthesis of ,,-trihydropolyfluoroalkyl chlorophosphates is by reacting ,,-trihydropolyfluoroalkyl dichlorophosphites and bis-(,,-trihydropolyfluoroalkyl) phosphites with sulfuryl chloride. It has been found that in three-coordinated polyfluoroalkyl phosphites, the high electronegativity of the polyfluoroalkyl groups hinders cleavage of the latter on reaction with sulfuryl chloride, thereby facilitating the formation of oxidation products.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 146–149, January, 1988.     

Prostanoids: LXXVII. Synthetic Approaches to Sterically Overcrowded Cyclopentenones

Condensation of (±)-5-allyl-2,3,5-trichloro-4,4-dimethoxy-2-cyclopentenone with phenylethynylmagnesium bromide in THF gave (±)-5-allyl-2,3,5-trichloro-4,4-dimethoxy-1-phenylethynyl-2-cyclopenten-1-ol which chemoselectively reacted with ozone at the terminal double bond, affording (±)-2,3,5-trichloro-5-formylmethyl-4,4-dimethoxy-1-phenylethynyl-2-cyclopenten-1-ol. Oxidation of the latter with H₂CrO₄ yielded a mixture of the expected product, (±)-5-carboxymethyl-2,3,5-trichloro-4,4-dimethoxy-1-phenylethynyl-2-cyclopenten-1-ol, and anomalous profound oxidation product, (±)-2,3,5-trichloro-5-carboxymethyl-4,4-dimethoxy-1-(2-oxo-2-phenylacetyl)-2-cyclopenten-1-ol. Attempts to remove protective methoxy groups in these compounds under standard conditions were unsuccessful.     

Steroid glycosides from the starfishEchinaster sepositus

Two new steroid glycosides, which have been called echinasterosides B₁ and B₂ have been isolated from the starfishEchinaster sepositus. Using chemical transformations (methylation, hydrolysis) and also spectral methods (¹H and¹³C NMR spectroscopy and GLC-MS) the complete chemical structure of B₁ has been established as 15-acetoxy-5-cholestane-3,4,6,8,24-pentaol 24-O[O-(2)O÷ methyl--D-xylopyranosyl)-(13)--L-arabinofuranoside] (I) and that of glycoside B₂ as 5-cholestane-3,4,6,8,15,24-hexaol 24-O-[O÷(2-O-methyl--D-xylopyranosyl)-(13)--L-arabinofuranoside] (II).Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Pirodnykh Soedinenii, No. 2, pp. 246–249, March–April, 1987.     

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.     

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.     

Formation of Supramolecular Polymers Constructed by Cyclodextrins with Cinnamamide

-Cyclodextrin having cinnamamide at 6- or 3-positions (6-CiNH--CD, 3-CiNH--CD) and -cyclodextrin with cinnamamide on 6-position (6-CiNH--CD) have been prepared. Supramolecular structures were formed in the solid state or aqueous solutions and characterized by measurements of NMR and vapor pressure osmometry (VPO). The results indicate that 6-CiNH--CD formed insoluble supramolecular polymers in the solid state, while 6-CiNH--CD and 3-CiNH--CD formed supramolecular complexes in aqueous solutions. 6-CiNH--CD was found to form a dimer in an aqueous solution. 3-CiNH--CD formed intermolecular complexes to give supramolecular polymers. The differences of the position of guest part on cyclodextrins caused to give a variety of supramolecular structures in aqueous solutions.     

Synthesen von 2-Anilinocyclopentanonen

The syntheses of the 2-anilinocyclopentanones2 a–2 e in yields about 50% by reaction of 2-chlorocyclopentanone with 4-chloroaniline, N-methyl-4-chloroaniline, ,,-trifluoro-3-toluidine, N-methyl-,,-trifluoro-3-toluidine and 3,4,5-trimethoxyaniline, are described.     

Mono- and sesquiterpenoids of the oleoresin ofAbies nephrolepis. Crystal structure of (+)-β-cedrol

The composition of the mono- and sesquiterpenoids from the oleoresin of the Khingan fir has been studied. Thirteen monoterpenoids have been identified — bornyl acetate, -terpenyl acetate, geranyl acetate, citronellyl acetate, -fenchyl acetate, linalool, geraniol, terpineol-4, -terpineol, -fenchol, borneol, sabinene hydrate and thymol methyl ether; and 19 sesquiterpenoids — -longipinene, longicyclene, longifolene, -copaene, -ylangene, sibirene, -and -selinenes, - and -cadinenes, -muurolene, caryophyllene, -humulene, - and -bisabolenes, ar-curcumene, nerolidol, bisabolol, and -cedrol. The crystal structure of -cedrol has been investigated by x-ray structural analysis.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 41–45, January–February, 1985.     

Heterylimidazoles IV. Homolytic dissociation of hexaaryldimidazolyls and their heterocyclic analogs

The rate constants and activation energies for homolytic dissociation of 2,2-di[ ()-naphthyl]-, 2,2-diquinolinyl-, and 2,2-di(9-acridinyl)-4,4,5,5-tetraphenyldiimidazolyls in toluene in the presence of,-diphenyl--picrylhydrazine were determined. The degrees of dissociation of the diimidazolyls were found. The effect of substituents on the stability of imidazolyl radicals is discussed.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1536–1539, November, 1974.     

Substitution of the halogen atoms in α-halogenonitro compounds of the aliphatic series 4. Interaction of carbonyl compounds with ethyl chloronitroacetate under the conditions of the Reformatsky reaction

The reaction of ethyl chloronitroacetate with carbonyl compounds of the aliphatic series under the conditions of the Reformatsky reaction in ether, THF, or benzene does not proceed with the substitution of the chlorine atom, but by the scheme of the Anri reaction with the formation of ethyl -nitro--chloro--hydroxycarboxylates. The reaction proceeds via the intermediate formation of the zinc salt of ethyl chloronitroacetate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2729–2732, December, 1989.     

Study of the rotational isomerism about the C-O bond in six-membered secondary-tertiary diols

We have determined the spectroscopic characteristics, the dipole moments, and the Kerr constants of the stereoisomers of the secondary-tertiary diols of the cyclohexane and bicyclo [4.1.0]pentane series: 3,4-dihydroxy-3-carane (I), 3,4-dihydroxy-3-methylnorcarane (II), 3,4-dihydroxy-3-methylnorcarane (III), 4, 5-dihydroxy-3-methylcyclohexene (IV), 3,4-dihydroxy-3-carane (V), 3,4-dihydroxy-3-methylnorcarane (VI), 3, 4-dihydroxy-3-carane (VII), and 3,4-dihydroxy-4-methyl-3-carane (VIII). It was found that the cis diols are more polar than their trans isomers. It was shown by electrical and electrooptical methods that rotamers with a gauche orientation with respect to the tertiary C-O are stable relative to those containing the diol at the ordinary C-C bond of the ring.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 619–625, March, 1991.     

Über die Darstellung von 3β, 16α-und 3β, 16β-Diacetoxy-5α-pregnan-20-on

Zusammenfassung Die Synthese von 3, 16-Diacetoxy-5 -pregnan-20-on (VI) aus 3-Acetoxy-5 -pregn-16-en-20-on und eine verbesserte Darstellung von 3, 16-Diacetoxy-5 -pregnan-20-on (III) aus 3-Acetoxy-pregna-5, 16-dien-20-on werden beschrieben.     

Untersuchungen über Phenthiazinderivate. 10. Mitteilung

Zusammenfassung Es wurde ein allgemein anwendbarer Weg zur Herstellung von in -Stellung basisch substituierten 4,10-Trimethylenphenthiazinen durch Umsetzung der aus den -Hydroxyverbindungen erhaltenen -Bromverbindungen mit sekundären Aminen angegeben. Für das in der Literatur bekannte -Amino-4,10-Trimethylen-phenthiazin wurden neue Darstellungen beschrieben.     

Order and disorder in mixed metal linear chains: The homo and heterobimetallic EDTA (M(H2O)4OIOII)[M′(EDTA)] · 6H2O complexes (M = Mg,Mn, Co,Zn and Ni; M′ = Co,Ni, Cu and Zn)

Summary Polymetallic solid solutions of the ethylenediaminetetracetic acid (EDTA) and six divalent metal ions exist in the range: MgMnCoZnNiCu(EDTA) · 6H₂O where + + + + + =2, 01, 0,,2, 0, 1.This type of structure is characterized by the presence of two different octahedral carboxylate-bridged coordination sites forming infinite zig-zag chains. Visible and i.r. spectra and t.g.a. analysis show that there is occupational preference for the two coordination sites in the crystalline structure.Due to this preference, and also to the structural features, the heterobimetallic MM(EDTA) · 6H₂O compounds constitute a structurally new class of materials which can be described as ordered alternating-heterobimetallic polymeric coordination complexes.     

Transformed steroids

A preparative method for 9a-hydroxylation of ⁵-3-hydroxysteroids using the fungi ofCircinella sp. 10Kh-1220 not capable of modifying theA ring has been developed. It is established that the yields of the main and the side products greatly depend on the transformation conditions, mycelium age, and the structure of the steroid substrate. Under the optimal transformation conditions novel 9-hydroxysubstituted derivatives of androstenolone, pregnenolone, 16-dehydro-16,17-epoxy-, and-16-methoxypregnenolone have been obtained in 36–80 % yields.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 737–743, April, 1994.     

Zur Kenntnis der gemeinsamen Einwirkung von elementarem Selen und gasförmigem Ammoniak bzw. Ethylenimin auf Ketone

Elemental sulfur reacts with ketones and gaseous ammonia at room temperature yielding thiazoline-3 in excellent yields. Under the same conditions elemental selenium does not react at all. Attempts using the known techniques which have been applied in improving the reactivity of slowly reacting ketones in thiazoline-3-synthesis have been unsuccessful (Exp. No. 1–17). The reaction of -halogenketones with sodiumhydrogenselenide to synthesize -hydroselenoketones gives only the original ketones and selenium in almost quantitative yields (No. 18–23). The same is observed with -haloketones and sodium ore magnesium-diselenides (No. 24–45). The explanation of these unexpected results is the strong reducing power of the hydrogenselenide (No. 46–52). Even -bromoketones with activated bromine (i.g. by phenyl groups) were reduced by sodiumhydrogensulfide giving red undefinite oils. However, -chloroketones give -mercaptoketones in excellent yields (No. 53–61). Hydrogenselenide reduces -mercaptoketones to sulfur and ketones in the presence of triethylamine (No. 62–67). Also the transformation of -selenocyanketones to ,-diketodisenides by alkali or the oxidative hydrolysis of selenium-BUNTE salts does not work and gives elementary selenium only. Studies about the concomitant reaction of elementary selenium and ethylenimine on ketones were continued (No. 68–82).

     

13C NMR spectra of acetylated hederagenin glycosides

The¹³C NMR spectra of acetylated derivatives of the following hederagenin glycosides have been studied hederagenin 3-0--L-arabinopyranoside, hederagenin 3-0-[0--L-rhamnopyanosyl-(12)--L-arabinopyranoside], hederagenin 3-0-[0--D-glucopyranosyl-(12)--L-arabinopyranoside], hederagenin 28-0--D-glucopyranoside, and hederagenin 28-0-[0--L-rhamnopyranosyl-(14)-0--D-glucopyranosyl-(16)--D-glucopyranoside]. The spectra give information about the monosaccharide composition, the position of attachment of the carbohydrate chain, and the configurations of the glycosidic bonds, and, in some cases, the orders of the bonds.Pacific Ocean Institute of Bioorganic Chemistry of the Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 359–362, May–June, 1980.     

Chemistry of the lipids

Conclusions 1. A. new route for the synthesis of optically active ,-diglycerides has been developed.2. D- and L-, -Distearins and D-, -dilinolenin have been synthesized from the readily accessible L- and D--O-tritylglycerols.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 210–214, 1969     

Triterpene glycosides of Pulsatilla dahurica structures of glycosides A,B, C,and D

The isolation of four triterpene glycosides from the roots of the dahurian anemonePulsatilla dahurica (Fisch. ex DC) Spreng, is described together with their identification, on the basis of chemical transformations, spectral characteristics, and literature analogies, as hederagenin 3-O--L-arabinoside, hederagenin 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranoside], hederagenin 3-O--L-arabinopyranoside 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside], and hederagenin 3-O-[O--D-glucopyranosyl-(14)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside].Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 349–356, May–August, 1992.     

Structure of karatavicin

Summary The synthesis of the following 1, 4-diphosphoinositides has been effected: the - (, -distearoyl) glyceryl ester of myoinositol 1, 4-diphosphate (VI) or (VII) and 1, 4-bis-[ - (, -distearoyl) glycerylphosphoryl] myoinositol (VIII).Khimiya Prirodnykh Soedinenii, Vol. 2, No. 4, pp. 230–233, 1966