Alkaloids ofHaplophyllum foliosum. II.

In addition to the alkaloids known previously from this plant, haplofoline and folifine, from the epigeal part ofHaplophyllum foliosum we have isolated norgraveoline with mp 288–289°C (decomp. from acetone), and myrtopsine with mp 201–202°C (from chloroform), [α]_D-5° (c 0.05; methanol), which were first obtained fromHaplophyllum dubium andMyrtopsis sellingii, respectively. We have confirmed by the PMR-spectroscopic method the positions of the substituents in the dihydrofuran ring of myrtopsine suggested previously on the basis of biogenetic considerations. In addition, it has been established that the substituents are present in the trans form. This is the first time that myrtopsine has been detected in plants of the genusHaplophyllum.     

Triaziridine. 9. Mitteilung. Ringöffnungen von Triaziridinen

Triaziridines. Ring Openings of Triaziridines Eleven triaziridine derivatives were heated at 60° in CDCl₃ to obtain information on the tendency towards, resp. the resistance to, ring opening of the N₃-homocycle by thermolysis. Among these triaziridines, there are three which contain, as one of the substituents, a methoxycarbonyl group (ester derivatives 1 , 5 and 16 ), three a methyl group (methyl derivatives 18 , 24 , and 26 ), three an H-atom ( 14 , 27 , and 30 ), and two a negative charge ( 31 and 32 ). The other two substituents in each of these four classes of triaziridines are trans-located i-Pr groups ( 1 , 18 , 27 , and 31 ), cis-located i-Pr groups ( 5 , 24 , 14 , and 32 ), and a 1,3-cis-cyclopentylidene group ( 16 , 26 , and 30 ). As major products these mild thermolyses, we isolated : from the trans-ester 1 and from the annellated ester derivative 16 , the 1-acyl-azimines 2 and 17 , respectively, from the cis-ester 5 , the 3-acyl-triazene 4 , from the trans-methyl derivative 18 , the (E)-diazene 19 , and hexamine 21 , from the cis-methyl derivative 24 the 2-methylazimine 25 , both from the trans- and cis-H-derivatives 27 , and 14 , respectively, the H- triazene 13 and, finally, both from the trans-and cis-anion 31 and 32 , respectively – after protonation the H-triazene 13 and – after methylation – the methyl-triazene 33 . The same thermolysis of the annellated methyl and H-derivatives 26 and 30 , respestively, resulted only in decomposition. These results can be uniformly interpreted with a primary opening of the triaziridine ring by rupture of one of the two types of N? N bonds lending to azimines or triazenide anions. Some of the azimines were isolable, namely 2 , 17 , and 25 , and one was spectroscopically observable as an intermediate, namely 11 on the way to the triazene 4 . The other azimines are plausible intermediates to the isolated products, namely 15 on the way to 13 , and 22 on the way to 19 and 21 . The triazenide anion 28 is the evident intermediate on the way to 13 or to 33 . The annellated azimines are assumed not be formed from 26 and 30 , or then to be be decomposed under the conditions of their formation. We conclude that the triaziridine derivatives 1, 16 , and 18 underwent thermal ring opening between N(1) and N(2), while the derivatives 5 , 14 , 24 , 27 , 31 , and 32 were ruptured between N(2) and N(3); no conclusion was possible on the ring opening of the derivatives 26 and 30 . The predominant formation of the (Z)-azimine 2 from the trans-triaziridine 1 , and of the (E)-isomer 3 – among the two azimines – from the cis-triaziridine 5 suggests a stereospecificity in the triaziridine ring openings. This would, however, not be expected to be observable in the products from the other triaziridines, since both N? N bonds of the azimine 25 and of the anion 28 probably rotate rapidly and since the secondary trans formations of the other primary products are not able to retain configurational information.     

Aristoserratin,ein neues Indolalkaloid aus Aristotelia serrata W.R.B. OLIVER und A. peduncularis (LABILL.) HOOK. F. 178. Mitteilung über organische Naturstoffe

Aristoserratine, a New Indole Alkaloid from Aristotelia serrata W.R.B. OLIVER and from A. peduncularis (LABILL .) HOOK . F. The new indole alkaloid aristoserratine (2) has been isolated from Aristotelia. Its structure and absolute configuration were elucidated on the basis of spectroscopic data.     

Berberis alkaloids. XXIII. Structure of turcberine

Berberine, magnoflorine, palmatine, columbamine, jatrorhizine, epiberberine, berbamine, O-methylisothalicberine, armepavine, corypalline, glaucine, and corydine and the new alkaloid turcberine have been isolated fromBerberis turcomanica Kar., and the structure of turcberine has been established. Apart from berberine, this is the first time that any of these alkaloids have been isolated from this species of barberry, while this is the first time that corydine and armepavine have been isolated from the genusBerberis.Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences. Tashkent. Andizhan State Medical Institute. Translated from Khimiya Prirodnykh Soedeninii, No. 1, pp. 77–81, January–February, 1993.     

Berberis alkaloids. XV. Structure of bargustanine

Bargustanine (I), belonging to a new type of isoquinoline alkaloids, has been isolated from the phenolic fraction of the total alkaloids from the roots ofBerberis vulgaris L. Its structure has been established by chemical and spectral methods.Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Andizhan State Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 44–47, January–February, 1993.     

Acetylenchemie. 9. Mitt. Anellierte imidazole aus N-propinylamid-vorstufen

The Compound 2-(N-Formyl-N-prop-2′-inyl)aminopyridine was cyclised in boiling formic acid to 3-methylimidazo[1,2-a]pyridine, with 3-methylene-2H-imidazo[1,2-a]pyridine as the intermediate. Under similar conditions the 1,3-diprop-2-inylpyrimido[4,5-b]quinoline-2,4-dione resulted from 1-methylimidazo[1,2-a]quinoline-4-carbonic acid-N-2-prop-2′-inylamide and from the 1-prop-2′-inylbenzo[b][1,8]naphthyridin-2-one the 1-methylbenzo[b]imidazo[1,2,3-ij]naphthyridine-4,7-dione as a new ring system, was obtained.     

Pyrimidines. 73. Synthesis of acetylpyrimidines

It is shown that the use of benzene as the solvent in the preparation of 2- and 4-acetylpyrimidines from cyanopyrimidines via the Grignard reaction makes this reaction a practical method for the preparation of pyrimidinyl ketones. Preparatively convenient methods for the preparation of 4-acetylpyrimidine from 4-ethylpyrimidine through the -oximino derivative and 5-acetylpyrimidine from 4,6-dichloro derivatives of pyrimidine are proposed.See [1] for communication 72.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 958–962, July, 1981.     

Structure investigations by P.A.C.

The perturbed angular correlation /P.A.C./ technique is employed to investigate the structures of barium ferrite and barium hexaferrite using radioactive¹³³Ba /10.7 Y/ as a probe. The quadrupole interaction frequencies /W_Q'S/ are found to be 9.68 and 12.02 Mrad sec^–1 for barium ferrite and barium hexaferrite, respectively, showing a drift from usual cubic structure.     

Haloaldehyde polymers. IX. Polybromodichloroacetaldehyde

Bromodichloroacetaldehyde was synthesized by two methods. The first synthesis started from chloral, which was allowed to react with Ph₃P and the resultant compound brominated and hydrolyzed to give bromodichloroacetaldehyde in an overall yield of 60%. Purification by repeated distillation from P₂O₅ gave polymerization grade bromodichloroacetabldehyde. Bromodichloroacetaldehyde could also be synthesized by bromination of dichloroacetaldehyde diethyl acetal. The yields of this synthesis were only 20–30%, and the aldehyde could not be purified readily to give polymerization grade monomer. Bromodichloroacetaldehyde could be homopolymerized at ?30°C with anionic and also some cationic initiators to a polymer which was insoluble and did not melt but degraded to monomer above 200°C. The ceiling temperature of the polymerization was ?15°C in 1M solution. Bromodichloroacetaldehyde could also be copolymerized with isocyanates, primarily aryl isocyanates, and also with chloral.     

Cardenolide glycosides ofCheiranthus allioni. XV. Glucocheiranthoside

Another new cardenolide glycoside has been isolated from the plantCheiranthus allioni Hort., and has been named glucocheiranthoside. Its chemical structure has been established as 3β-(4′-O-β-D-glucopyranosyl-β-D-gulmoethylpyranosyloxy)-14-hydroxy-19-oxo-5β,14β-card-20(22)-enolide. State Scientific Center for Drugs, Ukraine, 310085, Kharkov, USSR. ul. Astronomicheskaya, 33. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 269–271, March–April, 1994.     

Polysaccharides of Polygonatum. VII. A glucofructan from P. sewerzowii

A glucofructan has been isolated from the rhizomes ofPolygonatum sewerzowii Bunge and has been called pseverin. According to its chemical and spectral characteristics, pseverin is a polysaccharide containing both inulin, 2 1, and leven, 2 6, glycosidic bonds. The problem of the correlation between the molecular structure of a glucofructan and its supermolecular organization has been considered. X-radiographic and electron-microscope studies have been made of pseverin and its acetate. It has been established that on precipitating from solution pseverin forms globular particles which aggregate to give elongated necklace-like formations. Fine lamellar structures are characteristic for the acetate.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 15–20, January–February, 1986.     

Cover Picture: Angew. Chem. Int. Ed. 12/2002

The cover picture shows the thermally induced shape‐memory effect for a covalently cross‐linked polymer network. The polymer in its temporary shape (cube, picture on top) is heated from room temperature up to 70°C. Within 60 seconds the sample recovers its memorized, permanent shape of a nearly planar foil (picture on top left). The visual change of the material from opaque to transparent is caused by the melting of crystallites of the switching segments. The scheme in the center of the picture illustrates the molecular mechanism of the shape‐memory effect. The shown polymer network, which is synthesized from poly(ε‐caprolactone)dimethacrylate as macromonomer, is one of the first polymer systems that have specifically been developed for applications in the biomedical field. The net points (black) determine the permanent shape while the crystallites (blue) stabilize the temporary shape. More on the current state and the potential of this technology can be found in the review by A. Lendlein and S. Kelch on p. 2034 ff.     

Iridoidglucoside aus Leucocarpus perfoliatus G. DON. 174. Mitteilung über organische Naturstoffe

Iridoidglucosides from Leucocarpus perfoliatus G. DON . The known iridoid glucoside boschnalosid (1) was isolated from Leucocarpus perfoliatus in addition to the hitherto unknown yuheinosid, for which structure 2 was deduced.     

Calcia-supported lanthanide oxides. I. Preparation and characterization

Ln₂O₃-CaO systems, where Ln=La, Sm, have been prepared by impregnation of calcia with aqueous solutions of Ln nitrates or by mixing both oxides. Decomposition at 1073 K leads to a slight decrease in the specific surface area when starting from Ln₂O₃, but to a sharp decrease when starting from the nitrates.     

Alkaloids ofHaplophyllum foliosum. II.

In addition to the alkaloids known previously from this plant, haplofoline and folifine, from the epigeal part ofHaplophyllum foliosum we have isolated norgraveoline with mp 288–289°C (decomp. from acetone), and myrtopsine with mp 201–202°C (from chloroform), []_D-5° (c 0.05; methanol), which were first obtained fromHaplophyllum dubium andMyrtopsis sellingii, respectively. We have confirmed by the PMR-spectroscopic method the positions of the substituents in the dihydrofuran ring of myrtopsine suggested previously on the basis of biogenetic considerations. In addition, it has been established that the substituents are present in the trans form. This is the first time that myrtopsine has been detected in plants of the genusHaplophyllum.Institute of the Chemistry of Plant Substances of the Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 613–616, September–October, 1981.     

Temperature drop turbidity. IV. Polystyrene

The molecular weight distribution of fractionated and unfractionated polystyrene samples has been determined by temperature drop turbidimetry, in which polymer is precipitated from dilute solutions in cyclohexanol by progressively cooling from 388 to 310 K. Estimates of the molecular weight averages and the polydispersities, obtained by calibration of the temperature of initial onset of precipitation, T_i, and the weight-average molecular weight were low, but could be substantially improved by correcting for concentration changes during precipitation. An empirical procedure correlating the breadth of turbidity-temperature curves to the logarithm of the polydispersity, as measured by gel permeation chromatography, appeared to be a simpler method of characterizing the polymer samples and as accurate as the computational methods above.     

Berberis alkaloids. XXXVII. Investigation of the alkaloids ofB. oblongata andB. integerrima. Crystal structure of 8-trichloromethyldihydroberberine

Two species of Berberis have yielded 10 isoquinoline alkaloids. In addition to known bases, two artifacts have been isolated — 8-trichloromethyldihydroberberine (I) and 8-trichloromethyldihydropalmatine. An x-ray structural analysis has been made of (1).Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 889–893, November–December, 1996. Original article submitted April 15, 1996.     

Indole derivatives. 126. Substituted nitrotryptamines

A preparative method has been developed for obtaining substituted nitrotryptamines from the corresponding nitrophenylhydrazones of -phthalimidobutyraldehyde.For communication 125, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1206–1210, September, 1984.     

Glykoside von Marsdenia erecta R. Br. 2. Mitteilung: Versuche zur Strukturbestimmung der Genine. Glykoside und Aglykone, 330. Mitteilung

Structures for the genins of the ester glycosides of Marsdenia erecta are suggested. They are based on the behaviour in alkaline hydrolysis of these ester glycosides, their NMR. and mass spectra and ORD. data. All genins are derived from three acyl-free pregnane derivatives, i.e. drevogenin-P ( 1 ), 17 β-marsdenin ( 3 ) and marsectohexol ( 7 ). The structure of 1 is known, 3 and 7 are new compounds, i.e. 3 = 3β,8β,11α,12β,14β-pentahydroxy-Δ⁵-pregnen-20-one and 7 = 3β,8β,11α,12β,14β,20ξ-hexahydroxy-Δ⁵-pregnene. Formulae 13–17 were attributed to the acyl-genins A-1, A-2, A-3, A-4 and A-5, but only two of them were pure compounds, i.e. acyl-genin A-3 = 11,12-di-O-tiglyl-17β-marsdenin ( 15 ) and acyl-genin A-5 = 11,12-di-O-acetyl-marsectohexoi ( 17 ). Acyl-genin A-1 is a mixture of the two esters 13a + 13b derived from drevogenin-P, and similarly acyl-genin A-2 is a mixture of the esters 14a + 14b derived from 17β-marsdenin. The poorly characterised acyl-genin A-4 is most probably a mixture of the esters 16a + 16b , also derived from 17β-marsdenin.     

Phytoecdysteroids of Rhaponticum carthamoides. II. Rhapisterone B

A new ecdysteroid (rhapisterone B) has been isolated from the seeds ofRhaponticum cathamoides (Willd.) Iljin. (familyCompositae). It has been shown that it is 2β, 3β, 11α, 14α, 20R, 24ξ-hexahydroxy-5β-cholest-7-en-6-one. Institute of the Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 806–808, November–December, 1991.