Phytoecdysones ofRhaponticum integrifolium II. Integristerone A

Summary A new phytoecdysone — integristerone A — has been isolated from the flower heads ofRhaponticum integrifolium. It has been shown that it is 1,2,3,14,20R,22R,25-heptahydroxy-5-cholest-7-en-6-one.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 813–819, November–December, 1977.     

Phytoecdysones ofRhaponticum integrifolium III. Integristerone B

Summary From the flower heads ofRhaponticum integrifolium we have isolated a new phytoecdysone — integristerone B. It has been shown that it is 1, 2, 3, 5, 14, 20R, 22R, 25-octahydroxy-5-cholest-7-en-6-one.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 457–463, July–August, 1978.     

Isolation of ecdysterone from the inflorescences ofRhaponticum integrifolium

A method has been developed for isolating ecdysterone from the inflorescences ofRh. integrifolium. The yield is 0.15% on the weight of the raw material.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 667–668, September–October, 1979.     

Phytoecdysteroids ofRhaponticum carthamoides

From the roots with rhizomes of the plantRhaponticum carthamoides Willd) Iljin Compositae), in addition to integristerone A, ecdysterone, polypodin B, 2-deoxyecdysterone, and 24(28)-dehydromakisterone A, we have isolated the new compounds ecdysteron3–2,3-monoacetonide (I), ecdysterone 20,22-monoacetonide (II)) and rhapisterone (III): I — C₃₀H₄₈O₇, mp 232–233° (ethyl acetate-methanol) [] _D ²⁰ +56.4±2° (c 0.0; methanol); II — C₃₀H₄₈O₇, mp 227–229° (ethyl acetate-methanol), [] _D ²⁰ +60.1±2° (c 1.3; methanol); III — C₂₉H₄₈O₇, mp, 241–242° (ethyl acetate-methanol), [] _D ²⁰ +30±2° (c 0.1; dioxane). The structure of (III) was established on the basis of spectral characteristics as 2, 3, 14, 20R, 22R, 23-5-stigmast-7-en-6-one. Details of the PMR, mass, and IR spectra of all the compounds and of the CD of rhapisterone are given.Institute of the Chemistry of Plant Substances of the Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 681–684, September–October, 1987.     

Phytoecdysones ofAjuga turkestanica. III. The structure of turkesterone

Summary From the roots ofAjuga turkestanica (Rg1.) Briq. family Labiatae a new phytoecdysone — turkesterone — has been isolated. It has been shown that it is 1120R-dihydroxyecdysone.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 466–470, July–August, 1975.     

Isolation of ecdysterone from the roots ofRhaponticum carthamoides

The solubility of ecdysterone in individual solvents and mixtures has been studied. A method has been developed for isolating ecdysterone from the roots ofRhaponticum carthamoides. Extraction from the raw material was carried out with methanol. The catty oils and tanning and resinous substances were eliminated from the concentrated and water-diluted extract by treatment with chloroform. The combined ecdysteroids were extracted from the purified aqueous solution with chloroform-isopropanol (1:1). They were freed from pigments by chromatography on alumina (Brockmann activity grade II) with elution by methanol-chloroform (1:2). The product was recrystallized from methanol-ethyl acetate (1:9), giving 0.05% (on the weight of the raw material) of ecdysterone.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirornykh Soedinenii, No. 4, pp. 528–529, July–August, 1980.     

Phytoecdysones ofSilene praemixta. II. Premixisterone

The structure of premixisterone (I) — a new ecdysteroid fromS. praemixta M. Pop. (Caryophyllaceae) — has been established. Compound (I) has the composition C₂₇H₄₄O₅, mp 110–112°C (from C₂H₅OH + H₂O), [] _D ²⁴ 0 ± 4° (c 0.85; MeOH), 202 nm (log 3.35), _max ^KBr 3415 cm^–1 (OH), 1710 cm^–1 (C=0), and does not contain the ⁷-6-keto grouping that is characteristic of natural ecdysteroids. The acetylation of (I) with (CH₃CO)₂ in Py gave the amorphous 3,22-diacetylpremixisterone (II), C₂₁H₄₈O₇. Compound (I) has the structure of 3,14,22R,25-tetrahydroxy-5-cholest-8-en-6-one. The IR, PMR, and mass spectra of (I) and (II) are given.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 797–799, November–December, 1979.     

Tin(IV) porphyrin complexes. Crystal structures of meso-tetraphenyl-porphyrinatotin(IV) diacetate, bis(dichloro-acetate), bis(trifluoroacetate) and diformate, and structural correlations for tin(IV) porphyrin complexes with O-bound anionic ligands

Structures of four tetraphenylporphyrinatotin(IV) bis(carboxylato) complexes [Sn(tpp)(OCOR)₂] have been determined by single crystal X-ray diffraction. All complexes have typical octahedral geometry. The average Sn-N bond lengths for R = CH₃, CHC1₂, CF₃, and H are 2.091 ?, 2.084 ?, 2.082 ?, and 2.086 ?, respectively. The Sn-0 bond lengths are 2.096 ?, 2.091 ?, 2.109 ?, and 2.090 ? respectively. These bond lengths and those of all other reported Sn(tpp) complexes of O-bound anionic ligands are compared. There is an inverse correlation between the Sn-N and Sn-O bond lengths, indicating that stronger electron donation by the axial anionic ligand results in an expansion of the porphyrin core. Correlation of the Sn-O bond lengths with the pK_a of the conjugate acids of the axial ligands shows that the stronger the acid, the longer the Sn-0 bonds, indicating that the bonding is dominated by electrostatic effects.     

Phytoecdysones ofSilene praemixta. I. Silenosterone

In addition to known ecdysteroids (2-deoxy--ecdysone and 2-deoxyecdysterone) fromSilene praemixta (Caryophyllaceae) we have isolated new ones — premixisterone and selenosterone (I), C₂₇H₄₂O₇, mp 115–117°C (from MeOH), [] _D ²⁸ +86.9 ± 2° (c 0.92, MeOH), yield 0.003%. The acetylation of (I) with (CH₃CO)₂O in Py gave 22-acetyl-selenosterone (II), C₂₉H₄₄O₆, mp 210–212°C (MeOH-C₆H₁₄), [] _D ²⁷ +45.5 ± 3° (c 0.16; MeOH). On the basis of physiocochemical and spectral characteristics it has been established that (I) has the structure of 14,22R,25-trihydroxy-5-cholest-7-ene-3,6-dione. The IR, PMR, and mass spectra of (I) and (II) are presented.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 793–797, November–December, 1979.     

Carbohydrates ofAllium. IV. Glucofructans ofAllium longicuspis

Water-soluble polysaccharides have been isolated from the bulbs ofAllium longicuspis Rgl. By fractionating the combined water-soluble polysaccharides, homogeneous polysaccharides with molecular weights of 15,500 and 5100 have been isolated. It has been shown by spectral and chemical methods that they consist of glucofructans of a mixed type containing glycosidic bonds of the inulin (2 1) and levan (26) types in a ratio of 2.1:1.Deceased.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 703–707, November–December, 1984.     

Synthesis of (Z)- and (E)-3-(2-chloropyridin-5-ylmethyl) oximino-(22E,24R)-ergosta-4,7,22-trienes and their oxidative transformations

(Z)- and (E)-3-(2-chloropyridin-5-ylmethyl)oximino-(22E,24R)-ergosta-4,7,22-trienes (5–6) were synthesized by chemical transformation of ergosterol. Several oxidative transformations of them were studied. It was found that oxidation of these compounds by chromium(VI) oxide formed the corresponding O-substituted 3-ketoximes of the mycosteroid (22E,24R)-ergosta-4,7,22-trien-3,6-dione (7) and (8), which contained α-chloropyridine fragments characteristic of biologically active neonicotinoids. It was shown that oxidation of 5 and 6 by selenium dioxide occurred with formation of the corresponding 9α-hydroxy derivatives 9 and 10.     

Alkaloids of far-eastern species ofThalictrum. IV

Summary The alkaloid composition of four far-eastern species ofThalictrum — Th. amurense, Th. contortum, Th. filamentosum, andTh. minus — have been studied, for the first time in the case of the first three species.Th. amurense contains -allocryptopine and thalictrisine, andTh. contortum contains -allocryptopine. Glaucine and thalicsimidine have been found inTh. filamentosum, and argemonine has been isolated fromTh. minus for the first time.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Scientific Center of the Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 788–791, November–December, 1976.     

The synthesis and x-ray structure of (N,N-dimethyldithiocarbamato)(n-butyl)diphenyltin(IV)

(N,N-Dimethyldithiocarbamato)(n-butyl)diphenyltin(IV), n-BuPh₂SnS₂NMe₂, crystallizes in the monoclinic space group P2₁/n with a 9.772(5), b 9.895(4), c 21.418(9) Å, β 95.81(3)⁰, V 2060 ų Z = 4, μ 14.4 cm⁻¹ The structure was determined by the heavy-atom technique from 3103 independent reflections measured at room temperature on an Enraf-Nonius four-circle CAD-4 diffractometer using monochromatized Mo-K radiation and refined to a final R value of 5.8%. The tin atom is essentially four-coordinated with a weak fifth tin-sulphur bond (Sn---S(2) 3.079(1) Å) considerably longer than the other (Sn---S(1) 2.466(1) Å). A comparison with the complex n-BuPhSn(C1)S₂CNEt₂ (Sn---S(1) 2.454(1) Å; Sn---S(2) 2.764(1) Å) suggests that enhanced steric factors are responsible for the preferential monodentate behaviour of the dithiocarbamate ligand in the title complex.