Molecular state of hydrochloric acid in its tributyl phosphate extracts

Using IR spectroscopy we have shown that at digerent equilibrium concentrations of HCl in aqueous phases, its tributyl phosphate @acts contain: 1) at C_Hcl ^a < 2.3 M, micelle-like associates H₅O₂ ⁺(H₂O)_n–2(TBP)_mCl^–·(H₂0·TBP)₂ (n 26 and m 13), the structure of micelles is discussed 2) at 2.3 M < C_HCl ^a < 5.6 M, dimer associates [H₅O₂ ⁺(H₂O)₂Cl^–(H₂O·TBP)₂]₂; 3) at 5.6 M < C_HCl ^a < 8.5 M, H-bonded molecular fragments H₅O₂ ⁺(TBP)_2/3Cl^–(A); and 4) at C_HCl ^a > 8.5 M, considerable amounts of the H₃O⁺ tisolvate start to form in molecular fragments H₃O⁺(TBP)_1/3Cl ^–(B) H-bonded with the nearest neighbors. At C_Hcl ^a > 5.6 M, almost no free TBP molecules occur in the extracts and a structured liquid forms from the A fragments; and at C_Hcl ^a > 8.5 M, from the B fragments.Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturmoi Khimii, Vol. 34, No. 5, pp. 72–79, September–October, 1993.Translated by K. Shaposhnikova     

Phytoecdysteroids of plants of the genus Silene. XVI. Viticosterone E 22-O-benzoate from Silene wallichiana

A new phytoecdysteroid, viticosterone E 22-O-benzoate (I), C₃₆H₅₀O₀, mp 147–149°C (methanol-water), [] _D ²⁰ +63.2° (methanol), has been isolated from the epigeal organs ofSilene wallichiana Klotzsch. The alkaline hydrolysis of (I) led to viticosterone E and benzoic acid. The acetylation of (I) gave the 2,3-diacetate (II), C₄₀H₅₄O₁₁, mp 152–153°C (methanol-water), [] _D ²⁰ +65.5° (methanol). Details of 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. 4, pp. 546–549, July–August, 1988.     

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.     

Synthetic and kinetic studies on copper(II), nickel(II) and cobalt(III) complexes of 1,4,7,10,13-pentaazacyclohexadecane ([16]aneN5)

Summary The pentadentate macrocycle 1,4,7,10,13-penta-azacyclo-hexadecane [16]aneN₅=(3)=L} has been prepared and a variety of copper(II), nickel(II) and cobalt(III) complexes of the ligand characterised. The copper complex [CuL](ClO₄)₂, on the basis of its d-d spectrum, appears to be square pyramidal, while [NiL(H₂O)](ClO₄)₂ is octahedral. The copper(II) and nickel(II) complexes dissociate readily in acidic solution and these reactions have been studied kinetically. For the copper(II) complex, rate=k_H[complex][H⁺]² with k_H =4.8 dm⁶ mol^–2s^–1 at 25 °C and I=1.0 mol dm^–3 (NaClO₄) with H=43 kJ mol^–1 and S ₂₉₈ =–89 JK^–1 mol^–1. Dissociation rates of the copper(II) complexes increase with ring size in the order: [15]aneN₅ < [16]aneN₅ < [17]aneN₅. For the dissociation of the nickel(II) complex, rate=k_H[Complex][H⁺] with k_H=9.4×10^–3 dm³mol^–1 s^–1 at 25 °C and I =1.0 mol dm^–3 (NaClO₄) with H=71 kJ mol^–1 and S ₂₉₈ =–47 JK^–1mol^–1.The cobalt(III) complexes, [CoLCl](ClO₄)₂, [CoL(H₂O)]-(ClO₄)₃, [CoL(NO₂)](ClO₄)₂, [CoL(DMF)](ClO₄)₃ (DMF=dimethylformamide) and [CoL(O₂CH)](ClO₄)₂ have been characterised. The chloropentamine [CoCl([16]aneN₅)]²⁺ undergoes rapid base hydrolysis with k_OH=1.1× 10⁵dm³ mol^–1s^–1 at 25°C and I=0.1 mol dm^–3 (H=73 kJ mol^–1 and S ₂₉₈ =98 JK^–1 mol^–1). Rapid base hydrolysis of [CoL(NO₂)]²⁺ is also observed and the origins of these effects are considered in detail.     

Production of a pyridine derivative of grosshemin

Summary The reaction of pyridine and hydrochloric acid with grosshemin in the presence of acetic anhydride forms a substance with the composition C₂₀H₂₄O₄NCl · H₂O, mp 160–165°C, [] ₂₀ ^D + 71.23 (c 1.33; water), for which structure (II) is proposed.All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 306–309, May–June, 1976.     

Products of the ozonolysis of epitorulosol

The structure of the products of the ozonization of epitorulosol [13S-labda-8(20),14-diene-13,19-diol] (I) has been established. Compound (I) (1 g) was ozonized at –30°C in 100 ml of absolute CH₃OH until saturation. The O₃ was driven off by nitrogen, 1 ml of (CH₃)₂S was added at –10°C, and the mixture was stirred for 1 h each at –10, 0, and 20°C and was worked up, and the product (1.13 g) was chromatographed on a column containing 45 g of silica gel. The following were eluted in the order of increasing polarity: 420 mg of 19-hydroxy-8,13;8,14-diepoxy-13S-15,20-bisnorlabdan-14-one (II), mp 141.5–142.5°C (from petroleum ether), [] _D ²³ –63° (c 3.1); 255 mg of 8,13;8,14-diepoxy-13S-15,20-bisnorlabdane-14,19-diol (III), characterized in the form of the diacetate (IV) with mp 100–107°C (from petroleum ether); and 117 mg of 19-hydroxy-14,15,20-trisnorlabdane-8,13-dione (V), mp 82–83°C [from petroleum ether-diethyl ether (1:1)], [] _D ²⁶ –40° (c 1.7). The same products but in different ratios were formed on the ozonization of (I) in CH₂Cl₂-Py or in hexane followed by decomposition of the ozonide by heating with H₂O. The []_D values were measured in CHCl₃. Details of the IR and PMR spectra are given.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishinev. Institute of Organic Chemistry, Siberian Branch of the USSR Academy of Sciences, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 524–527, July–August, 1987.     

Analytical application of atomic emission and atomic absorption spectrometry for the determination of imidazoline derivatives based on formation of ion-associates with sodium cobaltinitrite and potassium ferricyanide

Ion-association complexes of Naphazoline HCl (I), Tolazoline HCl (II) and Xylometazoline HCl (III) with [Co(NO₂)₆]^3– and [Fe(CN)₆]^3– were precipitated and the excess of the unreacted iron or cobalt comples was determined. A new method using atomic emission and atomic absorption spectrometry for the determination of the above drags in pure solutions and in pharmaceutical preparations is given. The drugs have been determined in the ranges 0.98–14.76, 0.78–11.80 and 1.12–16.80 g/ml solutions of I, II and III. respectively, using [Co(NO₂)₆]^3–], with mean relative standard deviations of 0.4–1.5% and 1.92%–19.68, 1.52–5.68 and 2.24–22.4 g/ml solutions of I, II and III, respectively using [Fe(CN)₆]^3– with mean relative standard deviations of 0.6–1.6%. The recovery values of 98.12–101.26% indicate high precision and accuracy.     

Coumarins fromPhlojodicarpus sibiricus

Phlojodicarpin [8-(2,3-epoxy-1-hydroxy-3-methylbutyl)-7-methoxycoumarin, C₁₅H₁₆O₅, mp 143–145°C, [] _D ²⁵ -37.5°], and isophlojodicarpin [8-(1,2-epoxy-3-hydroxy-3-methylbutyl)-7-methoxycoumarin, C₁₅H₁₆O₅, mp 132–134°C, [] _D ²⁵ -102.5°] have been isolated from the epigeal part ofPhlojodicarpus sibiricus. The results of the IR, UV, PMR, and mass spectrometry of these compounds are given.Institute of Chemistry, Academy of Sciences of the Mongolian Peoples' Republic, Ulan-Bator. Irkutsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 47–49, January–February, 1981.     

Structure and stereochemistry of pallinin

The roots ofFerula pallida Korov. have yielded pallinin, C₂₅H₃₈O₅, mp 79–80°C, []D²⁰ –148.5° (c 0.1; CHCl₃) — an ester of the new carotane alcohol pallinol and angelic acid. A structure and absolute configuration have been proposed for it on the basis of chemical transformations and spectral characteristics.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 53–56, January–February, 1986.     

Structure of korselimine

The new base korselidine with mp 272–274°C (methanol), []_D-75°, C₂₇H₄₃NO₂ (I), (ethanol), composition C₂₇H₄₃NO₂, has been isolated from the total alkaloids of the epigeal part ofKorolkowia sewerzowii Regel. As a result of the study of the chemical properties of the alkaloid itself and of its products of its transformation, the structure and partial configuration of korselamine have been established as (1,3,-dihydroxy-^8,14)-cevanene.Institute of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 44–46, January–February, 1989.     

Triterpene glycosides of alfalfa. III. Medicoside I

On the basis of chemical transformations and with the aid of physicochemical results, the structure of glycoside I isolated from the roots of the plantMedicago sativa has been established as hederagin 3-O-[O--L-arabinopyranosyl-(1 2)--D-glucopyranosyl-(1 2)--L-arabinopyranoside] 28-O--D-glucopyranoside. Compound (I), C₅₂H₈₄O₂₂, mp 210–212°C, [] _D ²¹ +38.4° (c 1.48; methanol). Acid hydrolysis of (I) led to hederogenin (II) — C₃₀H₄₈O₄, mp 326–330°C, [] _D ²³ +84.2° (c 0.19; pyridine. The Hakomorimethylation of glycoside (I) yielded the permethylate (IV) — C₆₅H₁₁O₂₂ [] _D ²³ +41.6° (c 1.79; methanol). The GLC analysis of the products of the methanolysis of compound (IV) showed the presence of 3,4,6-tri-O-methyl-D-glucopyranose, 2,3,4,6-tetra-O-methyl-D-glucopyranose, 3,4-di-O-methyl-L-O-arabinopyranose, and 2,3,4-tri-o-methyl-L-arabinopyranose. The alkaline hydrolysis of glycoside I gave compound (III) with mp 230–233°C, [] _D ²¹ +35.2° (c 0.21; methanol), which was identified as medicoside C. Details of the PMR spectrum are given for compound (IV) and of the IR spectrum for compound (I).Institute of the Chemistry of Plant Substances of the Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 607–610, September–October, 1986.     

Structure of zangezurine

A new base with []_D +208° (c 0.7; methanol) has been isolated from the combined nonphenolic alkaloids ofPapaver zangezuricum A. D. Mikheev, and has been called zangezurine (I). The acetylation of (I) with acetic anhydride in pyridine yielded O-acetylzangezurine (II). The structure of zangezurine has been established on the basis of the UV, IR, mass, PMR, and¹³C NMR spectra of (I) and (II).Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Pyatigorsk Pharmaceutical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 858–862, November–December, 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.     

Phytoecdysteroids of plants of the genusSilene X. Sileneoside E — 2-Deoxy-α-ecdysone 3-O-β-D-glucopyranoside — FromSilene brahuica

A new ecdysteroid has been isolated from the epigeal organs ofSilene brahuica Boiss. — 2-deoxy--ecdysone 3-O--D-glucopyranoside (I), C₃₃H₅₄O₁₀, mp 195–196°C, [] _D ²⁰ + 44.4° (methanol). The enzymatic hydrolysis of (I) led to 2-deoxy--ecdysone. Details of the IR, UV, mass, and¹H and¹³C NMR spectra of all the compounds are given.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 323–326, May–June, 1986.     

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.     

Triterpene glycosides of Astragalus and their genins. XX. Cycloorbigenin from Astragalus orbiculatus

A new genin — cycloorbigenin (I), C₃₀H₄₈O₅, mp 217–219°C, [] _D ²⁰ +28.3° (c 1.19; ethanol) has been obtained from a glycoside isolated from the epigeal parts of the plantAstragalus orbiculatus (Leguminosae), and on the basis of chemical transformation and spectral characteristics its structure has been established as 16,23:16,24-diepoxy-23(R),24(S)cycloartane-3,7,25-triol. The acetylation of (I) with acetic anhydride in pyridine yielded its diacetate (II), C₃₄H₅₂O₇, mp 148–150°C, [] _D ²⁰ +32.6° (c 0.92; methanol) and its triacetate (III), C₃₆H₅₄O₈, mp 137–139°C, [] _D ²⁰ +75° (c 0.4; methanol). The Jones oxidation of (I) led to a diketone (IV), C₃₀H₄₄O₅, mp 155–158°C, [] _D ²⁰ -73° (c 0.63; methanol). Details of the PMR, IR, and mass spectra are given for all the compounds.Institute of The Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 455–460, July–August, 1986.     

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.     

Crystal structure of ether solvate of octanuclear lutetium aluminohydride complex {[(Bu 2 t C5H3)LuH]4[Et2O·AlH4]2[AlH4]2}·Et2O

Overall X-ray structural analysis (XSA) of ether solvate crystals of the unusual octanuclear lutetium aluminohydride complex [(CpLuH)₄(Et₂O·AlH₄)₂(AlH₄)₂]·Et₂O (I) (Cp = 1.3–Bu₂ ¹C₅H₃) is reported. In complex I, four Lu atoms are located in vertices of an elongated tetrahedron; over each face of the tetrahedron there is one Al atom. Th'e octanuclear metal core of I is a very distorted cube with an approximate point symmeby D_2d formed by the bridging hydrogen bonds (covalent metal-metal bonds are absent in I). Each Lu atom in I (neglecting individual H and C atoms) has the same distorted square-pyramidal coordination with the -Cp ring in the apical position and three Al atoms and the nearest Lu atom in the base of the pyramid.Institute of Physiologically Active Substances, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 167–174, September–October, 1993.Translated by T. Yudanova