Esters of (1,2, 5-trimethyl-4-hydroxy-4-piperedyl)- and phenyl-(1,2, 5-trimethyl-4-hydroxy-4-piperidyl) acetic acids

The methyl ester of a new hydroxy acid of the piperidine series (-phenyl--(1,2, 5-trimethyl-4-hydroxy 4-piperidyl)acetic acid) has been prepared. Ethyl -(1,2, 5-trimethyl-4-hydroxy-4-piperidyl)acetate has been converted into the substituted pyridine, 1,1-diphenyl-2-(2-5-dimethyl-4-pyridyl)ethylene.     

Synthesis and1H NMR and13C spectroscopy of L-arabinopyranosyl biosides

Conclusions The 3-0- and 4-0-trityl ethers of the acetates of methyl -L- arid methyl -L-arabinopyranosides were synthesized. The glycosylation of the ethers with the aid of 3,4-di-0-acetyl-1,2-0-(1-exo-cyano)ethylidene--L-arabinopyranose and the subsequent deacetylation of the synthesized products yielded the disaccharides: methyl 4-0-(-L-arabinopyranosyl)-,methyl 4-0-(-L-arabinopyranosyl)-, and methyl 3-0-(-L-arabinopyranosyl)--L-arabinopyranoside; and methyl 4-0-(-L-arabinopyranosyl)-, methyl 4-0-(-L-arabinopyranosyl)-, methyl 3-0-(-L-arabinopyranosyl)-, and methyl 3-0-(-L-arabinopyranosyl)--L-arabinopyranoside.The assignment of the signals in the PMR and¹³C NMR spectra of the synthesized arabinopyranosyl biosides was carried out, allowing the determination of the type and configuration of the glycosidic bond by means of which the arabinopyranose residues are linked in the oligo- and polysaccharide chains.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 200–209, January, 1986.     

Synthesis of β-(2-aminopurin-9-yl)-α-alanines

The alkylation of 2-amino-6-chloropurine and of 2-amino-6-methylthiopurine with 1-bromo-2,2-diethoxyethane in dimethylformamide in the presence of sodium hydride has yielded 2-amino-6-chloro-9-(2,2-diethoxyethyl)purine and 2-amino-9-(2,2-diethoxyethyl)-6-methylthiopurine. By further transformations of these acetals, 6-substituted 2-aminopurin-9-ylacetaldehydes have been prepared from which, by the cyanohydrin synthesis -(2-amino-6-hydroxypurin-9-yl)--alanine (guanin-9-yl--alanine) and -(2-amino-6-mercaptopurin-9-yl)--alanine have been obtained. The synthesis of guanin-9-yl--alanine has completed the preparation of a series of -alanine derivatives of the five most important heterocyclic bases present in RNA and DNA.     

Steroid compounds of marine sponges. VII. Preparation of derivatives of sokotrasterol and halistanol sulfates and structure-activity interrelationships among these compounds

Five new sulfated derivatives of sokotrasterol and halistanol have been obtained: 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate); 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate) 23-palmitate; 24,25-dimethyl-5-cholestane-2,3,6-triol 3-(sodium sulfate); 24,25-dimethyl-5-cholestane-2,3,6-triol 6-(sodium sulfate); and 24,25-dimethyl-5-cholestane-2,3,6-triol 2,6-di(sodium sulfate). The inhibiting and membranolytic properties of the polysulfated steroids from sponges and their derivatives have been studied. It has been shown that physiological activity in this series of compounds depends on biphilicity.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 441–445, July–August, 1986.     

FT-Raman Spectra of 2-, 3-, and 4-Chlorostyrene Molecules Included in Cyclodextrins

FT-Raman spectra of 2-, 3-, and 4-chlorostyrene included in-cyclodextrin (CD),glycerol ether -CD, -CD,sulfated -CD, andglycerol ether -CD were recorded.In the inclusion complexes, the area of the vinyl(C=C) band decreased remarkably, whereasthe area of the phenyl (C=C) band increasedcompared to those of liquid 2-, 3-, and 4-chlorostyrene,respectively. From the results, the inclusion structures of2-, 3-, and 4-chlorostyrene were discussed.     

Synthesis of Ethyl cis- and trans-4-Chloro-5-oxo-1,2-diphenylpyrrolidine-2-carboxylate

Ethyl cis- and trans-4-chloro-5-oxo-1,2-diphenylpyrrolidine-2-carboxylate have been synthesized by the cyclization of ethyl N-(,-dichloropropionyl)-N-phenyl--aminophenylacetate.     

Versuche zur Darstellung von 4- Vinyltriarylmethylradikalen

Zusammenfassung Beim Versuch zur Darstellung von 4-Vinyltriarylmethylradikalen durch Umsetzung von 4-Vinyltriarylmethylchloriden mit Metallen entstehen intermediär Radikale, die jedoch sofort in einer mesomeren Form weiterreagieren, wobei Polymere mit Chinodimethan-Strukturen entstehen. Als Modell hierfür dient das gelbe 1,4-,-Diphenylchinodimethan, das aus 4-Methyltriphenylmethylchlorid und Pyridin in Lösung erhalten werden kann; es ist nicht in fester Form isolierbar und polymerisiert sich leicht zu Poly-1,4-,-diphenylxylylen, das durch IR- und NMR-Spektren identifiziert wird.

---

The attempted preparation of 4- vinyltriarylmethyl radicals

The attempted preparation of 4-vinyltriarylmethyl radicals by interaction of 4-vinyltriarylmethylchlorides with metals yielded unstable radical intermediates immediately undergoing further reaction to give polymers of a quinodimethane structuretype. 1,4-,-Diphenylquinodimethane, obtained from 4-methyltriphenylmethyl chloride and pyridine in solution, was used as a model compound. It cannot be isolated and readily polymerizes to give poly-1,4-,-diphenylxylylene identified by IR and NMR spectra.

---

---

Mit 2 Abbildungen     

Synthesis and study of L-arabinopyranosides of 5- and 6-nitroindoles

Condensation of 5- or 6-nitroindoline with L-arabinose gave 1--L-arabinopyranosyl-5 (or 6)-nitroindolines, which, after acetylation, dehydrogenation, and removal of the protective groups, are converted to 1--L-arabinopyranosyl-5(or 6)-nitroindoles and then to the corresponding amino derivatives. 1--L-Arabinopyranosyl-6-nitro-3-bromo-(iodo)indoles were obtained. The selective 2-O- and 3-O-deacetylation of 1-(2, 3, 4-tri-O-acetyl)--L-arabinopyranosyl-6-nitroindole was accomplished.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 224–229, February, 1979.     

Synthesis of 1,2-O-(1-cyanoethylidene)-3,6,2′,3′,4′-penta-O-acetyl-6′-O-trityl-4-O-α-D-glucopyranose

Conclusions We have synthesized 1,2-O-(1-cyanoethylidene)-3,6,2, 3,4-penta-O-acetyl-6-O-trityl-4-O--D-glucopyranosyl--D-glucopyranose, which is a potential monomer for polycondensation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2571–2573, November, 1977.     

3-β-D-ribofuranosides (C-nucleosides) of indoles

The possibilities of the direct glycosylation of indoles with glycosyl halides that do not contain participating groups in the 2 position were studied. The and anomers of the corresponding C-ribofuranosides were obtained by the reaction of indole or its 5-bromo and 5- or 6-nitro derivatives with 2,3-O-isopropylidene-5-O-p-nitrobenzoyl-D-ribofuranosyl bromide in refluxing benzene in the presence of silver oxide and molecular sieves. O-Substituted 3--D-ribofuranosides of indoles undergo isomerization to the 3--anomers. Mixtures of anomeric 3,2-deoxy-D-ribofuranosyl-6-nitroindoles and 1,2-deoxy-D-ribofuranosyl-6-nitroindoles were synthesized. The structures of the compounds obtained were confirmed by data from PMR, IR, UV, and circular dichroism spectroscopy and mass spectrometry.See [1] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 767–778, June, 1981.     

Transformed steroids. 189. Synthesis and transformations of 21-hydroxy-5α-H-pregnane 2′,2′-dimethyl-[16α,17α-d]-thioxalanes

In a continuation of the research on use of 20-keto-16,17-epoxysteroid 20-hydrazones for synthesis of 17-thio analogs of 20-ketosteroid 16,17-acetonides [2, 3], we synthesized 5-H-pregnane-3,16,21-trihydroxy-17-thiol-20-one 16,17-acetonide and found methods for its microbiological dehydrogenation and hydroxylation into ⁴-3-keto-and 9-hydroxy-⁴-3-keto derivatives.See [1] for Communication 188.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1182–1186, May, 1992.     

Fused Nitrogen-Containing Heterocycles: IV. 3-Benzoyl-2-oxo-1,2-dihydroquinoxaline Hydrazones and Flavazoles Derived Therefrom

3-Benzoyl-1,2-dihydroquinoxalin-2-one reacts with hydrazine and thiosemicarbazide to give the corresponding hydrazone and thiosemicarbazone. The reaction with arylhydrazines yields 3-(-arylazobenzylidene)-1,2,3,4-tetrahydroquinoxalin-2-ones which are tautomeric to the respective arylhydrazones. On heating in boiling acetic acid, the products of both types undergo intramolecular cyclocondensation with formation of 3-phenylpyrazolo[3,4-b]quinoxalines (3-phenylflavazoles). 3-Benzoyl-1,2-dihydroquinoxalin-2-one thiosemicarbazone gives rise to flavazole structure only in the presence of methyl 3-chloro-2-oxo-3-phenylpropionate as a trap of thiocarbamoyl moiety. The cyclization of 3-(-hydrazonobenzyl)-1,2-dihydroquinoxalin-2-one is accompanied by formation of quinoxalyl ketone azine.     

Circular Dichroism Spectra of 5- and 7-Bromo-6-ketosteroids

Circulardichroismspectra of 5- and 7-bromo-6-ketosteroidsof the cholestane and stigmastane serieswere studied. A negative Cotton effect corresponding to the n-* -transition of the ketone was observed in the CD spectra of 5-bromo-6-ketosteroids at 300 nm. The analogous Cotton effect was positive in CD spectra of 7-bromo-6-ketosteroids.     

Transformed steroids. 121. Synthesis of the δ-lactone of 3β-acetoxy-16α-hydroxy-6-oxo-24-nor-5α-chol-17(20)-en-23-oic acid

The synthesis of the ¹⁷⁽²⁰⁾-16 analog of natural chiogralactone is described. Attempts to introduce a 6-oxo group directly into the -lactone proved unsuccessful, since the first stage — saponification — took place with the formation of three products: the 3-hydroxy--lactone, the 3-hydroxy-²⁰⁽²²⁾-lactone, and the 15,17(20)-dienoic acid. The synthesis of the desired compound was effected from the ethyl ester of the 5,16-dienoic acid by the scheme 3-acetate3-tosylate6-hydroxy-3,5-cyclosteroid6-oxo-3,5-cyclosteroid6-oxo-5H--lactone. It has been shown that the cyclopropane ring in the 3,5-cyclosteroid -lactone is extremely stable under the conditions of acid treatments.N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 184–187, March–April, 1981.     

Phosphorus containing spiroaziridines

2-[Benzoylamino(dialkoxyphosphoryl)methyl]-2-chloro-4-butanolides are readily prepared by treating the corresponding half amidal of -chloro--formyl--butyrolactone with chlorophosphites. They undergo intramolecular nucleophilic substitution using sodium hydride to give previously unknown phosphorus containing aziridines.Kazan State Technological University, Kazan 420015. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1196–1198, September, 1997.     

Steroid transformations. Communication 169. Synthetic routes to 21-hydroxy(acetoxy)-2′,2′-dimethyl-[17α, l6α-d]-oxazolidine 20-ketosteroids

Conclusions 21-Hydroxy(acetoxy)-2,2-dimethyl-[17, 16-d]-oxazolidines of 20-ketosteroids can be synthesized by two methods. One of these is based on the ammonolysis of 16,17-epoxypregn-5-en-3,21-diol-20-one 20-carbethoxyhydrazone and can have preparative value.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 701–704, March, 1988.     

Structure of karatavicin

Summary The synthesis of the following 1, 4-diphosphoinositides has been effected: the - (, -distearoyl) glyceryl ester of myoinositol 1, 4-diphosphate (VI) or (VII) and 1, 4-bis-[ - (, -distearoyl) glycerylphosphoryl] myoinositol (VIII).Khimiya Prirodnykh Soedinenii, Vol. 2, No. 4, pp. 230–233, 1966     

Study of lactams. VI. Synthesis of 6-substituted purino [8, 9-11, 22]isoindol1nes

It is shown with 1-ethoxyisoindolenine that the reaction of lactim ethers with -amino--cyanoacetamide also extends to partly aromatized lactim ethers, although these react much less readily. Condensation of 1-ethoxyisoindolenine with -amino-cyanoacetamide gives 4-carbamido-5-aminoimidazo[1, 2-1, 2]isoindoline, from which a new series of purinoisoindioline derivatives is synthesized.For part V see [2].     

Oxidative transformations of labdane diols. III. Preparation of acids with a strobane skeleton from larixol

It has been shown that the oxidation of larixol with chromic acid mixture forms methyl 6-oxo-8,13-epoxystroban-14-oate, methyl 6-oxo-8,13-epoxystroban-14-oate, and 6,13-dioxo-14,15-bisnorlabd-7-en-17-oate.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 697–703, November–December, 1986.     

Quinazolines X. Synthesis of 6,6'-methylenebisdeoxyvasicinone and its homologs

Summary 6,6-Methylenebisdeoxyvacisinone and its homologs have been synthesized by the reaction of methylenebisanthranilic acid with lactams (-butyrolactam, -valerolactam, -caprolactam, and -chloro- and ,-dichloro--caprolactams). The condensation of anthranilic acid and its derivatives (4-nitro-, 5-bromo-, 5-iodo-, and 5-nitroanthranilic acids) with ,-dichloro--caprolactam has given seven-membered analogs of deoxyvasicinone containing two chlorine atoms in the polymethylene ring.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 544–547, July–August, 1977.