Some remarks on the periodical change of the stability constants of the lanthanide complexes

The correlations between the values of the lgK (K = stability constant of the lanthanide complex) and the reciprocal of the ionic radius 1/r or the sum of the ionization potentials ₁ ³ I for the lanthanide ions were reviewed for different ligands. A straight-line relationship (lgK – lgK)/lgK vs. (1/r – 1/r)/(1/r) or vs. ( ₁ ³ I – ₁ ³ I)/ ₁ ³ I was found within the tetrads La-Nd, Gd-Ho, and Er-Lu.

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Bemerkungen zum periodischen Wechsel der Stabilitätskonstanten von Lanthaniden-Komplexen

Zusammenfassung Es wurde eine Übersicht der Korrelationen zwischen den Werten von logK (K = Stabilitätskonstante der Lanthanidenkomplexe) und den reziproken Ionenradien 1/r oder der Summe der Ionisierungspotentiale ₁ ³ I für die Lanthanidenionen für verschiedene Liganden gegeben. Dabei wurde eine lineare Korrelation für (lgK – lgK)/lgK gegen (1/r – 1/r)/(1/r) oder gegen ( ₁ ³ I – ₁ ³ I)/_1/3 I innerhalb der Tetraden La-Nd, Gd-Ho und Er-Lu aufgefunden.

     

Reactions of pennogenin and related compounds. IV. Formation of (25R,22′R,25′R)-3β,3′β-diacetoxy-26,22′-epoxy-16,16′-bifurosta-5,20(22),5′,17′(20′)-tetraen-26′-ol from pennogenin diacetate under the action of BF3·Et2O

A new direction of the reaction of pennogenin diacetate with BF₃·Et₂O has been discovered in which a previously unknown dimeric steroid is formed — (25R,22R,25R)-3,3-diacetoxy-26,22-epoxy-16,16-bifurosta-5,20(22), 5,17(20)-tetraen-26-ol, the structure of which has been established as the result of an analysis of IR, UV,¹H and¹³C NMR, and mass spectra. A probable mechanism for the formation of the title compound from pennogenin diacetate is suggested.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Institute of Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 202–208, March–April, 1990.     

The structure of xanthalin

Conclusions From the roots ofXanthogalum purpurascens growing in the Transcaucasus, we have isolated a new coumarin, C₂₄H₂₆O₇ with mp 111–113°C, [] _D ²⁰ –164.2° (c 0.97; ethanol) which we have called xanthalin. On the basis of the NMR spectrum it has been established that xanthalin is 3, 4-diangeloyl-2, 2-dimethyl-3, 4-dihydropyrano-5, 6:6, 7-coumarin.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 5, pp. 280–283, 1968     

Spectral characteristics of C-methylflavones

A study has been made of natural C-methylflavones and their dealkylated analogues: 5-hydroxy-4,7-dimethoxy-7-methylflavone (noreucalyptin); 4,5,7-trihydroxy-6-methylflavone; 5-hydroxy-4,7-dimethoxy-6,8-dimethylflavone (eucalyptin); 4,5-dihydroxy-7-methoxy-6,8-dimethylflavone (sideroxylin); 4,5,7-trihydroxy-6,8-dimethylflavone; 4,5,6-trihydroxy-3-methoxy-8-methylflavone (silpin) and 3,4,5,6-tetrahydroxy-8-methylflavone.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 306–309, May–June, 1984.     

Reaction of succinonitrile with aliphatic amines

Conclusions The reaction of primary amines with succinonitrile leads to the formation of N,N,N,N-tetrasubstituted amidines and the liberation of 2 M of NH₃. The reaction of secondary amines with succinonitrile proceeds as an intramolecular condensation with the liberation of 1 M of NH₃ per mole of the dinitrile and the formation of the ^2,5–, -dialkylaminopyrrolene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2722–2725, December, 1973.     

Kinetics of the alkaline hydrolysis of flavonoid glycosides

Summary 1. In a study of the kinetics of the alkaline hydrolysis of flavone glycosides it has been found that derivatives of 3,3,4,5,7-pentahydroxyflavone hydrolyze faster than derivatives of 3,4,5,7-tetrahydroxyflavone and of 3,4,5,7-tetrahydroxy-3-methoxyflavone.2. In the hydrolysis of diglycosides of 3,3,4,5,7-pentahydroxyflavones the maximum amount of intermediate product is formed after 2 min (3,4,5,7-tetrahydroxyflavone glycoside), and in the case of 3,4,5,7-tetrahydroxy-3-methoxyflavone glycosides after 120–150 min.I. V. Kutateladze Institute of Pharmacochemistry, Academy of Sciences of the Georgian SSR, Tbilisi. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 646–649, September–October, 1977.     

New terpenoid coumarins from Ferula tadshikorum

Summary Two new terpenoid coumarins — tadzhiferin (I) and tadzhikorin (II) — have been isolated from the fruit ofFerula tadshikorum M. Pimen.On the basis of physicochemical and spectral investigations, the structure of 7-(9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin is proposed for (I) and that of 7-(4-acetoxy-9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin for (II).All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov State University. Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 593–599, September–October, 1976.     

Soluble polysaccharides of Rhodotorula flava

Conclusions 1. Xanthalin has been shown to have the structure of 2, 2-dimethyl-3, 4,-diangeloyloxy-3, 4-dihydropyrano-5, 6:6, 7-coumarin on the basis of the preparation of a number of derivatives and cleavage products.2. The following products of the alkaline hydrolysis of xanthalin have been isolated and characterized for the first time: (±)-3, 4-dihydroxy-3, 4-dihydroxanthyletin (isokhellactone), C₁₄H₁₄O₅, with mp 213–215° C and (–)-trans-3-hydroxy-4-methoxy-3, 4-dihydroxanthyletin (isomethylkhellactone, C₁₅H₁₆O₅, with mp 136.5–138° C and [] _D ²⁰ –47.7 (ethanol).Khimiya Prirodnykh Soedinenii, Vol. 6, No. 1, pp. 14–19, 1970     

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.     

Chlorsulfonierung von Aromaten mittels Malonsäurediamid-N,N′-disulfochloriden

Zusammenfassung Die Malonsäurediamid-N,N-disulfochloride1–4 übertragen beim Erhitzen in Benzol oder Toluol die SO₂Cl-Gruppe auf den Aromaten, wobei das Diamiddisulfochlorid in gasförmige Bruchstücke zerfällt. Das Massenspektrum von Isopropylmalonsäurediamid-N,N-disulfochlorid (1) wird diskutiert.

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Chlorosulfonation of aromatic hydrocarbons by means of malondiamide disulfochlorides

Malonamide-N,N-disulfochlorides (1–4) transfer their SO₂Cl-group to aromatic solvents if heated to reflux. Under these conditions the malonamide-N,N-disulfochlorides are cleaved into gaseous fragments. The mass spectrum of isopropylmalonamide-N,N-disulfochloride (1) is discussed.

     

Diacetylenic Derivatives of Fe2(CO)6(μ-EE′): Spectroscopic Investigations of Fe2(CO)6{μ-EC(H) = C(C≡ CMe)E′} (E = E′, E ≠ E′; E, E′ = S, Se, Te)

The diacetylenic adducts, Fe₂(CO)₆{-EC(H) = C(C CMe)E} (E = E, E E; E, E = S, Se, Te) (1–8) have been obtained from the room temperature stirring of Fe₂(CO)₆(-EE) with HC CC CMe in methanol solvent containing sodium acetate. Compounds 1–8 have been characterized by IR and multinuclear NMR (¹H, ¹³C, ⁷⁷Se, and ^l25Te) spectroscopy. Trends in the chemical shifts of ⁷⁷Se and ¹²⁵Te NMR spectra of Fe₂(CO)₆{-EC(H) = C(C CMe)E} with a variation of EE are discussed.     

A new terpenoid coumarin trans-diversin fromFerula litwinowiana

The results are presented of investigations into the structure of a new terpenoid coumarin with the composition C₁₉H₂₀O₄ with mp 96–98°C (from aqueous ethanol), differing from diversion by the trans position of one bond. On the basis of spectroscopic (IR and¹H NMR) results, the structure of 7-(3,7-dimethyl-5-oxoocta-3E,6-dienyloxy)coumarin is proposed for this substance.V. L. Komarov Institute of Botany, Academy of Sciences of the Azerbaidzhan SSR, Baku. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 360–362, May–June, 1987.     

New chiral acyclic analogs of 2′-deoxynucleosides

Convenient methods for the synthesis of chiral 2,3-seco-2-deoxynucleosides were developed. An isopropylidene protective group was used to block the 3,5-hydroxy groups in 2,3-seco-uridine. Conversion of the hydroxymethyl group to a methyl group was accomplished by chlorination with a mixture of CCl₄ and Ph₃P with subsequent reduction with n-Bu₃SnH. 2,3-seco-2-Deoxyuridine was obtained after deacetonation. The (S) enantiomer was similarly synthesized starting from 1-(-D-arabinofuranosyl)uracil. 3-O-tert-Butyldimethylsilyl-5-O-(p-monomethoxytrityl)-2,3-seco-2-deoxyuridine, which has optically active centers at C₍₁₎ and C₍₄₎, was also synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 822–826, June, 1988.The authors thank Professor M. Ya. Karpeiskii for his constant interest in this research.     

Investigations in the field of complex lipids

Summary 1. The synthesis of L-(+)--oleoyl--linoleoyl--glycerylphosphorylethanolamine has been effected.2. During the investigations the following substances were isolated and characterized: L--oleoyl--glycerylphosphoryl-N-phthaloylethanolamine and L---linoleoyl--glycerylphosphoryl-N-phthanoylethanolamine.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 2, pp. 80–83, 1966     

Application of the Arbuzov reaction to establish the structure of D-mannitol tricyclic triethyl triphosphite

Conclusions The previously expressed theory that the tricyclic triethyl triphosphite of D-mannitol is 2-ethoxy-4, 5-bis-(2-ethoxy-1, 3, 2-dioxaphospholan-4-yl)-l,3,2-dioxa-4-phospholane was corroborated on the basis of the differential-thermal analysis and³¹P NMR data.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1390–1395, June, 1972.     

Enthalpies of formation and O-O and C-O bond strengths in polyoxides RO x R′ and RO x

Bond strengths in RO-OOR, ROO-OH, and ROO-OOR (R, R = H, Me, Et, and Bu) molecules, calculated by the semiempirical quantum-chemical methods, were used to determine the enthalpies of formation of polyoxides RO _x R (x = 3, 4) and related radicals and the bond strengths (D/kcal mol^–1) in these molecules:D(ROOO-OR) = 33.2±0.9,D(ROOO-OH) = 37.5±0.7,D(R-O _x R) = 76.0±1.2,D(H-000) = 58.6,D(R-000) = 42.8±0.8. A new value of Benson's polyoxide thermochemical increment, _f H°[O-(O)₂] = 11.1±1.0 kcal mol^–1, was suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2190–2193, September, 1996.     

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.     

Five-membered 2,3-dioxo heterocycles: XLIX. Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-2-carboxylates with N-substituted 3-amino-5,5-dimethyl-2-cyclohexenones

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates react with N-substituted 3-amino-5,5-dimethyl-2-cyclohexenones to give 4-hydroxy-1-aryl-3-aroyl-6,6-dimethyl-1, 2,3,4,5,5,6,7-octahydro-1H,2H-indole-3-spiro-2-pyrrole-2,4,5-triones. The structure of the products was proved by the X-ray diffraction data for the 1-cyclohexyl derivative.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004, pp. 1840–1845.Original Russian Text Copyright © 2004 by Bannikova, Maslivets, Aliev.For communication XLVIII, see [1].     

Coumarins of theLibanotis buchtormensis

Conclusions From the roots ofLibanotis buchtormensis (Fisch.) D.C. have been isolated the furocoumarins bergapten, isoimperatorin, a pyranocoumarin, xanthogallol, and a new coumarin buchtormin C₁₉H₂₀O₅, for which the structure (+)-3-(,-dimethylacryloxy)-2,2-dimethyl-3, 4-dihydropyrano-5, 6:8, 7-coumarin has been proposed and confirmed by synthesis.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 3, pp. 145–149, 1968