Oxidative coupling of 5-membered heterocycles catalyzed by a Pd(II)-heteropolyacid system in dimethylformamide

Oxidative coupling of thiophene and 2-methylfuran to the corresponding dihetaryls in DMFA medium occurs in the presence of the homogeneous catalytic system Pd(II)-molybdovanodophosphoric heteropolyacid (HPA). The data obtained show that HPA may act as a reversible oxidant in polar aprotic media.

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, Pd(II)- 2- . , .

     

Flavonoids of inflorescences of Calendula officinalis

By column chromatography on polyamide sorbent, the inflorescences of pot marigold calendula have yielded eight substances of flavonoid nature: two aglycons — quercetin (C₁₅H₁₀O₇, mp 309–311°C) and isorhamnetin (C₁₆H₁₂O₇, mp 314–316°C); six glycosides, of which three have been identified as isoquercetin (C₂₁H₂₀O₁₂, [] _D ²⁰ –36° in methanol, mp 218–220°C), isorhamnetin 3-O--D-glucoside (C₂₂H₂₂O₁₂, [] _D ²⁰ –59° in dimethylformamide, mp 193–195°C), narcissin (C₂₈H₃₂O₁₆, [] _D ²¹ –28° in dimethylformamide, mp 180–182°C), and three substances that have proved to be new and have been called calendoflaside (C₂₈H₃₂O₁₅, [] _D ²¹ –85° in methanol, mp 192–195°C; calendoflavoside (C₂₈H₃₂O₁₆, [] _D ²⁰ –106° in methanol, mp 189–192°C), and calendoflavobioside (c₂₇H₃₀O₁₆, [] _D ²⁰ –105° in methanol, mp 194–197°C).All-Union Scientific-Research Institute of Drug Chemistry, Khar'kov. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 795–801, November–December, 1988.     

Crystal and molecular structure of muurolene and cadinene dihydrochlorides

An x-ray structural investigation ( Mo K2/ scanning for 2<50°, MLS in the anisotropic approximation) has been performed of cadinene dihydrochloride (I) (1213 reflections, R=0.053) and muurolene dihydrochloride (II) 1643 reflections, R=0.087). The crystals of (I) belong to the rhombic system with a=6.053(2), b=14.622(5), c=17.926(7) A, Z=4, sp. gr. P2₁2₁2₁, mp 117°C. The crystals of (II) belong to the monoclinic system, with a=9.842(4), b=11.627(6), c=13.677(9) Å, =95.10(4)°, Z=4, sp. gr. P2₁, mp 86°C. The six-membered rings of the molecules (I) and (II) have the chair conformation with equatorial alkyl groups. The chlorine atoms have the axial arrangement. The molecule of (I) has the 3,9-dichlorocadinane structure, and that of (II) the 3,9-dichlormuurolane structure. The increased mean length of the C-Cl bonds of 1.844 Å in the molecule of (I) and 1.879 Å in the molecule of (II) must be mentioned.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 52–57, January–February, 1981.     

Cardiac glycosides ofAcokanthera venenata

Six cardenolides have been isolated from the leaves ofAcokanthera venenata G. Don: AV-1, mp 252–255°C, [] _D ²⁰ +39.4° (MeOH); AV-2, mp 199–208°C, [] _D ²⁰ -59.3° (MeOH); AV-3, mp 269–275°C/300–304°C, [] _D ²¹ –69.8° (MeOH); AV-4, mp 279–289°C; AV-5, mp 222–225°, [] _D ²⁰ -64.3° (MeOH); and AV-6, mp 193–196°C [] _D ²⁰ –23.8° (MeOH — CHCl₃). AV-5 has been identified as acovenoside A. AV-3 is a new cardiac glycoside: it is 1-acetoxy-3-(4-O--D-glucosyl-3-O-methyl--L-talomethylosyloxy)-14-hydroxy-5, 14-card-20(22)-enolide (glucoacovenoside B).Khar'kov State Pharmaceutical Institute. All-Union Scientific Research Institute of Drug, Chemistry and Technology, Khar'kov. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 372–376, May–June, 1987.     

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.     

Triterpene glycosides and their genins fromThalictrum foetidum. V. Structure of cyclofoetoside B

A new glycoside (cyclofoetoside B) (I) has been isolated from the epigeal part of the plantThalictrum foetidum L. (Ranunculaceae). On the basis of chemical transformations and with the aid of physicochemical characteristics it has been established that cyclofoetoside B is 24S-cycloartane-3, 16, 24, 25, 29-pentaol 3-O--L-arabinopyranoside 16-O-[O--L-rhamnopyranoside-(1 6)--D-glucopyranoside], C₄₇-H₈₀O₁₇, mp 194–197°C (methanol); [] _D ²⁴ +15.7 ± 2° (c 0.88; pyridine). The enzymatic hydrolysis of (I) has yielded cyclofoetigenin B (III), 24S-cycloartane-3,16,24,25,29-pentaol 16-O--D-glucopyranoside, (IV), C₃₆H₆₂O₁₀, mp 223–225°C (acetone), [] _D ²⁴ +37 ± 2° (c 0.97; methanol) and 24S-cycloartane-3,16,24,25,29-pentaol 16-O-[O--L-rhamnopyranosyl-(1 6)--D-glucopyranoside, C₄₂H₇₂O₁₄, mp 229–231°C (methanol), [] _D ³⁰ +41 ± 2° (c 0.7; methanol). Details of the IR and¹H and¹³C NMR spectra of the compounds are given.Irkutsk Institute of Organic Chemistry, Academy of Sciences of the USSR. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Trashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 341–345, May–June, 1986.     

Preparation of 21-aldehydes of Δ17(20)-steroids

A method is described for the synthesis of 17(20)-unsaturated 21-aldehydes by the oxidation of 17-hydroxy-17-vinylsteroids with pyridine chlorochromate. The following compounds were obtained in the course of the investigation: 3-hydroxy-trans-pregna-5,17-dien-21-al acetate, mp 177–178°C (MeOH); trans-pregna-5,17(20)-diene-3,21-diol 3-acetate (I), mp 150–153°C (MeOH); the 21-acetate of (I), with mp 130–133°C (ether-hexane); 3-oxo-trans-pregna-4,17(20)-dien-21-al, with mp 130–132°C (MeOH); and 3-oxo-trans-pregna-4,17(20)-dien-21-cic acid, C₂₁H₂₈O₃, mp 261–263°C. The IR and NMR spectra of the substances obtained are given.All-Union Scientific-Research Institute of Pharmaceutical Chemistry, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 340–342, May–June, 1979.     

The structure of the flavonoids from Rhodiola algida. II

Summary New flavonoid glycosides have been obtained from the roots ofRhodiola algida: rhodalgin (I), composition C₂₀H₁₈O₁₁, mp 239–240°C; acetylrhodalgin (II) C₂₂H₂₀O₁₂, mp 223–224°C; diacetylrhodalgin (III), C₂₄H₂₂O₁₃, mp 208–209°C; and triacetylrhodalgin (IV), C₂₆H₂₄O₁₄, mp 230–231°C.It has been established that they have the following structures: (I), 3,4,5,7,8-pentahydroxyflavone 8-O--L-arabinopyranoside; (II), 3,4,5,7,8-pentahydroxyflavone 8-O-(3-O-acetyl--L-arabinopyranoside; (III), 3,4,5,7,8-pentahydroxyflavone 8-O-(2,3-di-O-acetyl)--D-xylopyranoside; and (IV), 3,4,5,7,8-pentahydroxyflavone 8-O-(2,34-tri-O-acetyl)--D-xylopyranoside. The -L-arabinopyranose and -D-xylopyranose are present in these compounds in the C1 conformations.In the performance of this investigation, the authors consulted O. S. Chizhov, and M. B. Zoltarev (N. D. Zelinskii Institute of Organic Chemistry of the Academy of Sciences of the USSR) and V. I. Sheichenko (All-Union Institute of Medicinal plants).All-Union Scientific-Research Institute of Medicinal Plants. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 712–720. November–December, 1975.     

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     

Structure and configuration of a new diterpenoid lactone fromLagochilus hirsutissimus

The epigeal part of the plantLagochilus hirsutissimus has yielded a new diterpenoid lactone — lagohirsidin, C₂₂H₃₄O₅, mp 144–145°C, [] _D ²² – 17.5° (c 1; ethanol). Reduction with LiAlH₄ has yielded a diol C₂₂H₃₈O₅, mp 165–166°C [] _D ²⁰ –1.2 (c 0.6; ethanol). Acid hydrolysis of the diol has led to the formation of lagochilin, C₂₀H₃₆O₅, mp 167–168°C, [] _D ²⁰ –3.9° (c 1; ethanol). The synthesis of lagohirsidin from lagochilin has been effected.V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 788–792, November–December, 1979.     

Artenolide — A new disesquiterpenoid fromArtemisia absinthium

A new steroid glycoside — alliospiroside B (I) — has been isolated from the collective fruit ofAllium cepa L. On the basis of chemical transformations and with the aid of physicochemical measurements it has been established that compound (I) has the structure of (25S)spirost-5-ene-1,3-diol 1-O-[O--L-rhamnopyranosyl-(1 2)--D-galactopyranoside. Compound (I) C₃₉H₆₂O₃, mp 200–202°C (from ethanol). [] _D ²⁰ –110.9±2° (c 1.01; pyridine) was obtained by extracting the collective fruit ofA. cepa with ethanol folowed by the column chromatographic separation of the combined glycosides on silica gel. The acid hydrolysis of (I) gave (25S)-ruscogenin (II), C₂₇H₄₂O₄, mp 189–191°C, [] _D ²³ –104.1±2° (c 0.98; pyridine). The¹H and¹³C NMR spectra are given for both compounds and the IR spectrum for compound (I).Institute of the Chemistry of Plant Substances of the Uzbek SSR, Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 589–592, September–October, 1986.     

Diaqua[N,N-di(2-carboxyethyl)-o-anisidinato]copper(II) Dihydrate [Cu(o-Andp)(H2O)2] · 2H2O: Synthesis and Crystal Structure

Crystals of [Cu(o-Andp)(H₂O)₂] · 2H₂O (where o-Andp^2–is -anisidine-N,N-di-3-propionate) were synthesized and studied using X-ray diffraction analysis. The crystals are triclinic: a= 12.063(1) Å, b= 12.483(3) Å, c= 13.586(2) Å, = 91.29(1)°, = 111.67(1)°, = 104.00(1)°, V= 1830.5(5) ų, space group P , Z= 2, and R= 0.0528 for 5965 reflections with I2(I). The two crystallographically independent complexes are isostructural. The tetragonal–bipyramidal coordination of copper(III) involves three O atoms, the N atom of the tetradentate ligand o-Andp^2–, and two O atoms from water. The aminodipropionate group of the ligand (average Cu–O 1.939 Å and Cu–N 2.051 Å) and one of the coordinated water molecules (Cu–O(w) 1.991 Å) lie in the equatorial plane. The second water molecule (Cu–O(w) 2.32 Å) and the methoxy O atom of o-Andp^2–(Cu–O 2.37 Å) are in the apical positions of the bipyramid.     

Crystal structure of the synthetic analog of radtkeite Hg<Subscript>3</Subscript>S<Subscript>2</Subscript>Cl<Subscript>1.00</Subscript>I<Subscript>1.00</Subscript>

The results of structural studies of the synthetic analog of the radtkeite mineral Hg₃S₂Cl_1.00I_1.00 are analyzed. The crystal structure of the compound has been refined; the unit cell parameters are a _m = 16.827(4) , b _m = 9.117(1) , c _m = 13.165(5) , = 130.17(2)°, V = 1543.3(8) ³, space group C2/m, Z = 8, R = 0.0527. A possible transition a ₀ = a _m; b ₀ = a _m + 2c _m; c ₀ = –b _m to the pseudo-orthorhombic F cell previously determined for radtkeite, where one of the angles ( ₀ ) is slightly different from 90° (89.55°), has been found. Each sulfur atom in the structure is bonded to three mercury atoms, forming SHg₃ umbrellas with distances 2.240(6) –2.474(8) and angles HgSHg 94.7(2)°–102.9(2)°. The SHg₃ fragments are linked through Hg vertices to form corrugated [Hg₁₂S₈] layers. The halogen atoms lie inside and between the [Hg₁₂S₈] layers; the distances are Hg-Cl and Hg-I 2.783(7) , 2.961(7) , and 3.083(4) –3.311(3) , respectively.Original Russian Text Copyright © 2004 by N. V. Pervukhina, S. V. Borisov, S. A. Magarill, D. Yu. Naumov, V. I. Vasiliev, and B. G. NenashevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 755–758, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Cardiac glycosides of Cheiranthus allioni. XIII. Glucoerycordin

From plains erysimum (Cheiranthus allioni) Hort., (Erysimum asperum) a new cardiac glycoside has been isolated which has been called glucoerycordin. Its chemical structure has been established mainly by stepwise hydrolysis and the identification of the hydrolysis products. Glucoerycordin C₄₁H₆₄ O₁₉, mp 131–135°C, [] _D ²⁰ –22.2 ± 3° (c 0.65; methanol) is 3-[O--D-glucopyranosyl-(1 4)-O--D-glycopyranosyl-(1 4)-gulomethylopyranosyloxy]-14,19-dihydroxy-5, 14-card-20(22)-enolide.All-Union Scientific-Research Institute of Drug Chemistry and Technology, Khar'kov. Khar'kov State Pharmaceutical Institute. Translated from Khimiya Prirodnykh, No. 1, pp. 73–75, January–February, 1989.     

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.     

Heating and quenching of metastable superconducting compounds with a plasma jet

Superconducting compounds, such as cubic -MoC_1–x, cubic -WC_1–x, hexagonal MoB₂, and cubic -TaN, which are metastable at room temperature, have been formed by heating and quenching of their respective equilibrium phases, such as hexagonal -MoC_1–x, hexagonal WC, rhombohedral Mo₂B₅, and hexagonal -TaN in a plasma jet. From calculations based on a simple model, the quenching rate of particles has been estimated to be 10⁵ deg s^–1.     

Triterpene glycosides ofAstragalus and their genins. XII. Askendoside B fromAstragalus taschkendicus

On the basis of chemical transformations and with the aid of physicochemical characteristics it has been established that a new glycoside of the cycloartane series — askendoside B (I) — isolated from the roots ofAstragalus taschkendicus Bge., is 20S,24R-epoxycycloartane-3,6,16,25-tetraol 3-0-[0--L-arabinopyranosyl-(1 2)-(3-0-acetyl--D-xylopyranoside)] 6-0--D-xylopyranoside, C₄₇H₇₆O₁₈, mp 215–218°C, [] _D ²⁰ –45.5° (c 1.1; pyridine). The acid hydrolysis of (I) yielded cyclosiversigenin (II) with mp 239–241°C, [] _D ²⁰ +54.5° (c 1.2; MeOH), and cyclosiversigenin 3-0--D-xylopyranoside (III) with mp 262–264°C, [] _D ²⁰ +41° (c 0.4; MeOH). The periodate oxidation of glycoside (I) followed by acid hydrolysis likewise led to (II) and to D-xylose. The alkaline hydrolysis of (I) yielded askendoside D (IV), with mp 235–236°C, [] _D ²³ –8.5° (c 1.0; pyridine). The Smith degradation of (I) led to (III). The IR and PMR spectra of (I) are given.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 457–460, July–August, 1983.     

Synthetic investigations in the field of the curare alkaloids

It has been shown that the compounds obtained previously corresponding in comparison to the -[4-(5-carboxymethyl-2-hydroxyphenoxy)3-methoxyphenyl]ethylamide of 4-benzyloxyphenylacetic acid have practically the same spectra and on further condensation with 3-bromo-4-hydroxy-5-methoxyphenylethylamine give an equilibrium mixture of diamide compounds. The difference in the physicochemical properties of the diphenyl esters and the diamides can be explained by steric differences. On cyclization, the diamides are converted into bis-dihydroisoquinoline compounds of the same elementary composition. The hydrochloride of 7-[2-acetoxy-5-(7-acetoxy-8-bromo-6methoxy-3, 4dihydroisoquinol-1-ylmethyl)phenoxyl)-1-(4-benzyloxybenzyl)-6-methoxy-3,4-dihydroisoquinoline, with mp 180–181° C, after saponification, intramolecular Ullman condensation, reduction, and stepwise methylation, was converted into isomeric tubocurarin iodides with mp 189–190.5° C, 164–166.5° C, 257–260.5° C, and 210–212° C, which were separated on the basis of their different solubilities in organic solvents and water.For part XII, see [1].