Alkaloids of Gentiana olivieri

Summary The separation of the chloroform fraction of the combined alkaloids ofG. olivieri according to basicities (pH 6.0 and 4.0) has yielded gentioflavine, gentiananine, and the new base oliveramine, C₂₀H₂₀N₂O₄. On the basis of its UV, IR, NMR, and mass spectra structure (I) has been put forward as the most probable for it.Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 64–67, January–February, 1973.     

Alkaloids ofGentiana. Structure of gentianadine and gentianamine

Summary 1. Gentianine and the three new alkaloids gentiananine, gentianadine, and gentianamine have been isolated fromGentiana turkestanorum andG. olivieri; gentianadine is identical with synthetic 4-(2-hydroxyethyl) nicotinic lactone.2. Gentianamine has the structure 5-vinyl-4-(1-hydroxymethyl-2-hydroxyethyl) nicotinic lactone.3. Dihydrogentianine has been converted into dihydrogentianamine.Khimiya Prirodnykh Soedinenii, Vol. 3, No. 2, pp. 182–187, 1967     

Alkaloids of Aconitum coreanum VIII. Structure of coryphidine

A new C₂₀-diterpene alkaloid of the coryphine type has been isolated from the plantAconitum coreanum (Levl.) Rapaics, and it has been called coryphidine. Its structure has been established on the basis of an analysis of IR and¹H and¹³C NMR spectra. This is the second diterpene alkaloid having a hexahydro-N-methylindole fragment at C-17. Coryphidine contains an imide grouping, which is unusual for a diterpene skeleton.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 243–246, March–April, 1992.     

Anomalous1H NMR spectra of 3,4-dihydroisoquinolines and related compounds

Solutions of 3,4-dihydro-6,7-methylenedioxyisoquinoline (1) and analogues2–5 and9 as well as isoquinolines7 and8 in certain samples of CDCl₃, CCl₄, DMSO-d₆ or acetone-d₆ gave rise to anomalous¹Hnmr spectra with extreme line broadening, signals due to protons at C-l and C-3 most often not being seen. The spectra of1 and3 were most striking in this respect.¹Hnmr spectra of the quaternary salt10 and the model schiff base11 were normal. Several hypotheses for the observed line broadening have been considered and rejected, a slow equilibrium1 ⇆13 being one of them. NaBH₄ reduction of1 and2 followed by mass spectrometric analysis of the crude tetrahydroisoquinolines16 and17 ruled out a slow equilibrium1 ⇆14 and2 ⇆15 as contributory cause for line broadening. The crude reduction products unexpectedly contained N-ethyl species22 and25. Their formation is rationalised     

A study of the alkaloids ofSaussurea salsa andS. elegans

Conclusions 1. In the extraction ofS. salsa andS. elegans, the condensation of the neutral substances with ammonia takes place with the formation of products of a basic nature.2. FromS. elegans a new alkaloid elegantine C₂₃H₂₉O₅N has been obtained the saponification of which has given tyramine and a sesquiterpene lactone.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 6, pp. 367–370, 1968     

Investigation of Aconite alkaloids

Summary The composition of the alkaloids in plants of the genus Aconitum —A. kirinense,A. altaicum, A. coreanum, andA. nemorosum — has been studied. Four new alkaloids of composition C₂₆H₄₁O₈N·HNO₃, C₃₅H₄₁O₁₀N·HBr, C₂₀H₂₅O₃N, and C₂₃H₂₉O₆N have been isolated.Khimiya Prirodnykh Soedinenii, Vol. 1, No. 2, pp. 113–116, 1965.     

The structures of chimganin and chimgin

Summary The roots ofFerula tschimganica Lipsky have yielded two new compounds with the compositions C₁₈H₂₄O₄ (mp 85°C) and C₁₇H₂₂O₃ (mp 155°C), which have been calledchimganin andchimgin. On the basis of their UV, IR, and NMR spectra and the products of alkaline hydrolysis, it has been shown that chimganin is the ester of 4-hydroxy-3-methoxybenzoic acid and chimgin that of 4-hydroxybenzoic acid with (+)-borneol.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 59–63, January–February, 1972.     

Synthesis, characterization and reactivity of oxomolybdenum(V) complexes with ONS and NNS donors

The monomeric oxomolybdenum(V) complexes, [MoOLCl₂]1a-1d [HL = S-benzyl/methyl 3-(2-pyridyl)methylenedithiocarbazate (1a and1b), or N-methyl-S-benzyl/methyl 3-(2-hydroxy phenyl)methylenedithiocarbazate (1c and1d) are synthesized by the reaction of MoOCl ₅ ²⁻ with HL ligands. All these complexes show magnetic moment of about 1.7 B.M. The complexes,1a and1b, exhibit rhombicg-tensor anisotropy (like xanthine oxidase) whilst1c and1d show axial spectrum. The above complexes undergo irreversible electrochemical reduction furnishing Mo(IV) species and the potentials are dependent on the S-substituents. Reactions of MoOX ₅ ⁻ (X = Cl or Br) with H₂L¹ [H₂L¹ = S-methyl 3-(5-R-2-hydroxyphenyl)methylenedithiocarbazate] (R = H, CH₃, Cl, Br) produce complexes of thiolatobridged dimers, [Mo₂O₂L ₂ ¹ X₂], which show sub-normal magnetic moments at room temperature. The metal-centred irreversible oxidation and reduction of these complexes show expected dependence on the R-substituents of the salicyl phenyl ring of the ligands.     

Glycosides of Erysimum

Summary The cardenolides of six species ofErysimum and ofSyrenia siliculosa have been studied. The cardiac glycosides erysimin and erysimoside have been found inE. altaicum, E. marschallianum, E. nuratensae, andS. siliculosa. In addition to these glycosides,E. diffusum has yielded desglucocheirotoxin, canescein, and a new cardenolide, erydiffuside,E. violascens has yielded gypsobioside, andE. cuspidatum has yielded a new glycoside cuspidoside.Khimiya Prirodnykh Soedinenii, Vol. 3, No. 2, pp. 173–178, 1967     

Condensed heterotricycles: Pyrido(1,2,3- de )(1,4)benzoxazines, pyrido(1,2,3- ef )(1,5)benzoxazepines and pyrido(1,2,3- fg )(1,6) benzoxazocines

Cyclization of N-(2-haloacyl)-8-hydroxy-l,2,3,4-tetrahydroqumolines4–7 and9 with alkali affords pyridobenzoxazinones21–24 and26 respectively and of the 4-chlorobutyramide13 with NaH, the benzoxazocinone31. Exposure of 3-chloropropionamide12 to NaH affords acrylamide15, benzoxazepinone28 or methyl benzoxazinone22 or mixtures thereof under various conditions.28 undergoes rapid base-catalysed ring contraction to22. NaH-catalysed ring closure of acrylamide15 affords mixtures of22 and28, while from the crotonamides16 and17, the methylbenzoxazepinones29 and30 are obtained preponderantly, the former amide yielding only traces of the ethyl benzoxazinone23.29 shows no propensity for ring contraction to give23. The cinnamoyl derivatives18,19 and20 are cyclized to benzyl benzoxazinones24,27 and25, respectively. The intermediacy of the phenyl benzoxazepinone39 in the formation of24 has been established by deuteration studies. Benzylidene benzoxazinone41 is obtained from dibromocinnamamide14 and propiolamide40. Dichloracetamides8 and10 undergo interesting ring closure to compounds45–54 upon treatment with amines. The course of electrophilic reactions of the lactams depends upon the ring size. Contribution No. 18 from Searle R & D Centre Presented at a symposium to felicitate Prof N S Narasimhan at the University of Poona, November 18–19, 1988     

Proton lability in the amino ligand of and the1H-n.m.r. spectra oftrans-dichloro(diethylamine)(π-ethene)platinum and related complexes

Summary The NCH ₂CH₃ region of the¹H-n.m.r. spectrum oftrans-PtCl₂(-C₂H₄)(NHEt₂) has been investigated and shown to contain inequivalent protons. A study has also been made in related amine complexes of the conditions under which Pt-N-CH ₂ protons are equivalent, NH-CH coupling takes place and¹⁹⁵Pt-N-CH coupling occurs.The lability of the N-H bond intrans-olefin-amine, carbonyl-amine, ethanide-amine and phosphine-amine complexes is also investigated and compared with that of the platinum-amine link.Trans-labilizing powers of-C₂H₄, CO, CH₂¯CH₂ and Ph₃P are compared.     

Highly stereoselective reduction of chiral α-keto-β, γ-unsaturated acetals: Synthesis of both epimeric allyl alcohols by proper choice of additive

Highly stereoselective reduction of chiral α-keto-β, γ-unsaturated acetals (1a-3a) into each two epimeric optically active allyl alcohols (1b-3b and1c-3c) was attained by LiAlH₄ using additive (LiBr, MgBr₂).     

Histones of the cotton plant. Molecular characteristics of histone H1

A characterization of the histones of two varieties of the cotton plant,Gossypium hirsutum andG. barbadense, has been given with the aid of various electrophoretic systems. Their molecular weights have been determined. An analysis has been made of the cleavage of histone H1 at tyrosine residues. The positive charge and the molecular length of histone H1 have been determined by the method of incomplete succinylation.V. I. Nikitin Institute of Chemistry, Academy of Sciences of the Tadzhik SSR, Dushanbe. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 491–497, July–August, 1986.     

The structure of the glucan of Arum korolkovii

A glucomannan has been isolated from the tubers ofArum korolkovii Regel. It has been shown that the polysaccharide contains O-acetyl groups and consists mainly of (1 → 4)-β-linked aldohexopyranose units of glucose and mannose in a ratio of 1:1.6. The nonreducing ends of the glucomannan are glucose residues, and branching is localized at C₂ and C₃ of mannose.     

The alkaloids ofStephania glabra

Summary l-Tetrahydropalmatine and stepharine have been isolated from the tubers ofStephania glabra obtained from India, andl-tetrahydropalmatine and cycleanine have been isolated from the tubers ofStephania cultivated on the Black Sea littoral of the Caucasus.The epigeal parts of the plant cultivated on the Black Sea littoral of the Caucasus have given cycleanine and an alkaloid A of composition C₁₉H₂₁O₄N the study of which is proceeding.Khimiya Prirodnykh Soedinenii, Vol. 1, No. 4, pp. 271–275, 1965     

A study of the oils of Ocimum basilicum and Cardaria repens

Summary The seed oils of the plantsOcimum basilicum andCardaria repens have been studied. Their physico-chemical properties and fatty acid and glyceride compositions have been determined. Both oils contain a hydroxy acid of undetermined structure. The oil ofOcimum basilicum contains an unusual trienic acid.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 7–11, January, 1971.     

Regioselective Friedel-Crafts acetylation of 5-hydroxyindole derivatives: synthesis of 4H-pyranoindol-4-one derivatives

The Friedel-Crafts acetylation of 5-hydroxyindole derivativesla-c regioselectively produced 6-acetyl-5-hydroxy-indole derivatives2a-c which were condensed with cinnamic acid using POC1₃ and dry pyridine to afford 5-cinnamoyloxy-6-acetyl-indoles3a-c. These upon Baker-Venkataraman transformation furnished 6-cinnamoylacetyl-5-hydroxyindoles4a-c which were cyclised separately with AcOH/HCl and Ac₂O/AcONa to 4H-pyrano-(2,3-f)indol-4-one derivatives5a-c and6a-c respectively.     

Oils of the seeds of Ziziphora pedicellata and Eremostachys molluceloides

Summary The fatty oils of the seeds of the wild speciesZiziphora pedicellata andEremostachys molluceloides (Labiatae) have been investigated. The glyceride, pigment, and hydrocarbon compositions of these oils and the fatty-acid composition of the oil ofZ. pedicellata have been determined.The oil ofE. molluceloides contains laballenic acid.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 324–328, May–June, 1975.