Synthesis of 2-aryl-3,4,5,6-bis(trimethylene) pyrylium salts and the corresponding pyridine bases

2-Aryl-3,4,5,6-bis(trimethylene)pyrylium perchlorates were obtained by acylation of cyclopentylidenecyclopentanone with aromatic acid chlorides in the presence of anhydrous aluminum chloride with subsequent treatment with 70% perchloric acid. The synthesized salts were converted to the corresponding pyridine bases.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1461–1463, November, 1972.     

Terpenoids of Crepis tectorum. Molecular and crystal structure of the sesquiterpene lactone 8-epideacylcynaropicrin

Sesquiterpene lactones of the guaianolide type — isolipidiol (I) and 8-epideacylcynaropicrin (II) — have been isolated from narrow-leaf hawk's-beard,Crepis tectorum L. On the basis of the results of an x-ray experiment the structure of (1R, 3S, 5R, 6R, 7R, 8R)-3,8-dihydroxy-cis,trans-guaia-4(15),10(14),-11(13)-trien-6,12-olide is proposed for (II).Institute of Organic Synthesis and Coal Chemistry, Kazakh Academy of Sciences, Karaganda. A. N. Nesmeynaov Institute of Organometallic Compounds, Russian Academy of Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 638–642, September–October, 1991.     

Colorimetric method for the simultaneous determination of chlorphenoxamine hydrochloride and anhydrous caffeine in pure and dosage forms with rose bengal

A rapid, simple and sensitive colorimetric method for the simultaneous determination of chlorphenoxamine HCl and anhydrous caffeine was developed, based on charge-transfer complex formation of the drugs with rose bengal in basic media of pH 9.0. The chlorphenoxamine HCl (I) complex was measured at 588 nm whereas anhydrous caffeine (II) was measured at 551 nm. The optimal experimental parameters for colour production were studied. Beer's law was obeyed in the concentration ranges 2–40 and 2–34 g ml^–1 for I and II, respectively. The Ringbom optimum concentration ranges were 3–36 and 3–30 g ml^–1 for I and II, respectively. The results obtained showed good recoveries of 100.2 ± 1.5 and 99.7 ± 1.3% with relative standard deviations of 0.37 and 0.47% for I and II, respectively. Applications of the method to representative pharmaceutical dosage forms are presented and the validity assessed by applying the standard addition technique.     

Pheromones of insects and their analogs. XX. Methyl-branched pheromones based on 4-methyltetrahydropyran.

A synthesis is proposed of 4,8-dimethyldecanal (VIII) — a pheromone of the flour beetlesTribolium confusum andT. castaneum. By heating 71.2 g of 4-methyltetrahydropyran (I), 83.2 g of AcBr and 1.57 g of ZnCl₂ (45°C), then 120°C, 2 h), 1-acetoxy-5-bromo-3-methylpentane (II) was obtained. The hydrolysis of 19.8 g of (II) (MeOH-H₂O, TsOH, 20°C, 15 h) gave 5-bromo-3-methylpentan-1-ol (III). From 18.1 g of (III) and 38.9 ml of 2,3-dihydropyran (Et₂O, TsOH, 20°C, 20 h) was obtained the 2-THPL ester of (III), (IV), which was converted into 3-methyloct-7-en-1-ol (V) by the treatment of the corresponding Grignard reagent with allyl bromide (THF, CuI-bi-2-pyridyl, 2°C, 4 h, Ar). The interaction of 1.42 g of (V) with Et₃Al (hexane, 20°C, Cp₂ZrCl₂, Ar) gave 3,7-dimethylnonan-1-ol (VI), boiling which with 48% HBr in the presence of concentrated H₂SO₄ gave 1-bromo-3,7-dimethylnonane (VII) which was then converted into the desired (VIII) by the reaction of the corresponding Grignard reagent with DMFA (0–2°C, 1 h; 20°C, 2 h; Ar). The characteristics of the compounds — yield (%), n_D (°C): (I), 79, 1.4340 (22); (III) 89, 1.4660 (23); (IV), 82, 1.4739 (23); (V), 85, —; (VI), 90, 1.4483 (20); (VII), 88, 1.4409 (22); (VIII), 88, 1.4589 (22). Details of the IR and PMR spectra of compounds (II)–(VII) are given.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, USSR Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 272–276, March–April, 1989.     

Alkaloids ofAndrachne rotundifolia

Summary 1. The content of total alkaloids in the hypogeal parts ofAndrachne rotundifolia C. A. Mey. (family Euphorbicease) is 0.2–0.3% and in the epigeal parts 0.06–0.08%.The total alkaloids in both the hypogeal and the epigeal parts ofAndrachne rotundifolia consist of five or six non-phenolic bases.2. Three individual substances have been isolated: andrachnine C₁₁H₁₇NO₂, which is a new alkaloid; base (II), giving a perchlorate with mp 139°–140° C; and base (III) with mp 135°–136° C.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 4, pp. 257–260, 1966     

Reactions in anhydrous hydrogen fluoride Communication 1. Conjugated halogenation of olefins

Conclusions A method was developed for the synthesis of chlorofluoroalkanes by the conjugated chlorination of olefins in anhydrous HF. The 2-chloroethyl cation formed in the chlorination of ethylene can make an electrophilic attack on benzene with formation of (2-chloroethyl)benzene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1065–1069, June, 1966.     

Insect pheromones and their analogues

A scheme has been developed for the synthesis of (R)-(–)-10-methyltridecan-2-one, the sex pheromone of the southern corn rootworm (Diabrotica undecimpunctata) using as the chiral synthon (R)-(+)-methylheptenal obtained by the hydroperoxide oxidation of the readily available (S)-(+)-dihydromyrcene.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 125–129, January–February, 1992.     

Crystal and molecular structures of 1,8-diacetyl-3-methyl-DL-allantoin

DL-Allantoin (I) has been isolated from an alcoholic extract of a marine spongeAxinellidae gen. sp., and derivatives of it have been obtained: 1, 8-diacetyl-DL-allantoin (II) and 1,8-diacetyl-3-methyl-DL-allantoin (III). The crystal and molecular structures of (III) have been established by X-ray structural analysis.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 422–426, May–June, 1988.     

Synthesis of (E)-dodec-3-en-1-yl acetate — The main component of sex pheromones of Scrobipalpa ocellatella and Scrobipalpopsis solanivora

(E)-Dodec-3-en-l-yl acetate — the main component of the sex pheromones ofScrobipalpa ocellatella andScrobipalpopsis solanivora — has been obtained by a three-stage synthesis from decanal and malonic acid. The overall yield of pheromone was 33% calculated on the initial aldehyde.A. S. Sadykov Institute of Bioorganic Chemistry, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 682–683, September–October, 1988.     

Proanthocyanidins of Rhodiola semenovii

The structures of two compounds previously isolated fromRhodiola semenovii, rhodokhinoside (I) and rhodikhim (II), have been established.Institute of the Chemistry of Plant Substances, Uzbek. Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 771–777, November–December, 1991.     

Alkaloids of Aconitum rubricundum

The known alkaloids isolappaconitine (I), 9-deoxylappaconotine (II), lycaconitine (III), puberaconitine (IV), lycoctonine (V), ranaconitine (VI), ajacine (VII), and septentriodine (VII), and an unidentified alkaloid with mp 203–205°C have been isolated from the epigeal part of the Far-Eastern plantAconitum rubricundum. Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 403–407, May–June, 1991.     

Chiroptical properties of steroid 1,3-diaxial diols in the presence of [Mo2(OAc)4]

Summary Bidentate complexes of dimolybdenum tetraacetate with 1,3-diaxial diols show Cotton effects around 490–540 nm (CD band I), 400–440 nm (II), 350–380 nm (III), 320 nm (IV) and 280 nm (V). The sign of the Cotton effect II can be predicted by a proposed sector rule. It seems that from the Cotton effects for cyclic 1,3-diols the absolute configurations or conformations can be obtained.A part of this material was presented at III-rd International Conference on CD Spectroscopy [1]     

Rational Combination of the Dissolution of Some Inorganic Compounds of Rare-Earth Elements with the Determination of Chemical Forms of Major Constituents in These Compounds

It was found that the major constituents (F^– and S^2–) in fluorides, sulfides, and sulfofluorides of rare-earth elements, and europium(II) in europium fluoride, can be determined titrimetrically. Peculiarities of the decomposition and analysis of initial samples of these compounds and samples after high-temperature treatment in vacuum were considered. The analytical procedures are based on the combination of the decomposition of the test materials using solutions of iodine (determination of S^2–), boric acid (determination of F^–), and vanadium(V) salts (determination of europium(II) salts) and the final titration of excess reagents that selectively reacted with a chemical form of the analyte. Potentiometry with an ion-selective electrode was also used in the determination of fluoride ions. The total concentration of rare-earth elements was determined by chelatometry.     

Structures of four new triterpene glycosides from the holothurian Cucumaria japonica

Four new triterpene glycosides of the holostane series have been isolated from an alcoholic extract of the economically important Pacific Ocean holothurianCucumaria japonica: cucumariosides A₁-2 (I), A₂-3 (II), A₂-4 (III), and A₄-2 (IV). The structures of these substances have been established by the methods of carbohydrate chemistry and¹³C NMR spectroscopy.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 787–793, November–December, 1990.     

Study of the electrical oxidation of 2,6-dimethyl-3,5-diethoxy-carbonyl-1,4-dihydropyridines in acetonitrile by means of a rotating disk electrode with a ring

It is shown that the electrochemical oxidation of esters of 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acids in anhydrous acetonitrile takes place as a one-electron process, while the final products of the transformations (pyridines or pyridinium salts) are formed as a result of disproportionation of the intermediate radicals. When 1–2% (by volume) water is added, the oxidation mechanism changes substantially, and the electrochemical process becomes a two-electron process.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1263–1267, September, 1980.     

New glycosides from the holothurian Cucumaria japonica

Four new compounds have been isolated from the fraction of weakly polar triterpene glycosides of the holothurianCucumaria japonica: cucumariosides A₁-2 (I), A₀-1 (II), A₀-2 (III), and A₀-3 (IV). The structures of these substances have been established by chemical and physical methods.Deceased.Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Scientific Center, Russian Academy of Sciences, Vladivostok. Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 242–248, March–April, 1993.     

Lipids of the leaf vegetables Spinacea oleracea,Latuca sativa,and Rumex acetosa

The class compositions of the lipids of leaf vegetables —Spinacea oleracea (variety Ispolinskii),Latuca sativa (variety Kucheryavets Odesskii), andRumex acetosa (variety Odesskii-17) have been studied. The compositions of their NLs (17 groups of individual compounds were identified), GLs (nine groups of compounds were found), and PhLs (seven groups of compounds have been found) have been determined by physicochemical methods of analysis. The maximum amount of the total lipids and also of the PhLs was possessed by the spinach. Among the FAs of the leaf vegetables, USFAs predominated.M. V. Lomonosov Technological Institute of the Food Industry, Odessa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 199–205, March–April, 1993.     

Isolation of ternary complex precursors and partially condensed␣intermediates to macrocyclic complexes of nickel(II) and copper(II)

Reaction in unheated solutions between metal salts, bis(3–aminopropyl)amine (dpt) and 2,6–diacetylpyridine (dap) gives the ternary complexes [M(dpt)(dap)]2+ (M=Ni or Cu), in which no Schiff-base condensation has occurred. Cyclisation requires long standing or heating. For tris(3–aminopropyl)amine and nickel(II), X-ray crystallography shows that reaction in MeOH can be stopped after condensation of one carbonyl and one amine group to give a coordinated open-chain hexadentate ligand, an intermediate in the formation of the fully condensed macrocycle. With the 2–(aminoethyl)-4–(butylamino)amine (ebt), the butylamine groups are involved in intermolecular condensation with carbonyl groups from adjacent units, giving oligomeric or polymeric complexes.     

Pharmaceutical formulation analysis of thalidomide by solid surface room temperature phosphorimetry

A rapid and simple method of analysis for thalidomide formulations has been reported based on solid surface room temperature phosphorimetry. Thalidomide phosphorescence was enhanced by Hg(II) ions deposited on paper substrates previously treated for background reduction. A calibration curve with a linear dynamic range of three orders of magnitude was obtained (1.37 × 10^–6 M – 10^–3 M) and a 1.8 ng absolute limit of detection was estimated. The recovery of the method was tested in pharmaceutical formulations containing thalidomide as the only active ingredient. The values obtained were 96.3 ± 6.6% (employing the calibration curve procedure) and 98.0 ± 5.3% (employing the standard addition procedure), which show the potential of the technique for the analysis of thalidomide in dosage forms.