Lability of the β-diethylaminoethyl group under the conditions of the formation of a pyrrole ring via the Knorr synthesis

The corresponding 3-acetyl- and 3-H-pyrroles are formed along with 2,4-dimethyl-3-(-diethylaminoethyl)-5-carbethoxypyrrole in the condensation of 3-(-diethylaminoethyl)pentane-2,4-dione with isonitrosoacetoacetic (I) and isonitrosomalonic (II) esters.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1643–1645, December, 1973.     

New polyhydroxysteroids and steroid glycosides from the far east starfishCeramaster patagonicus

Two new polyhydroxysteroids and five new glycosides were isolated from the starfishCeramaster patagonicus and their structures were elucidated: 5α-cholestane-3β,6α,15β,16β,26-pentol, (22E)-5α-cholest-22-ene-3β,6α,8,15α,24-pentol, (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β,4β, 6α,8,15β,16β,28-heptol (ceramasteroside C₁), (22E)-28-O-[O-(2,4-di-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β, 6α,8,15β,16β,28-hexol (ceramasteroside C₂), (22E)-28-O-[O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β,6α,8,15β,16β 28-hexol (eramasteroside C₃), (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-methyl-5α-cholest-22-ene-3β,4β,6α,8, 15β, 26-hexol (ceramasteroside C₄), and (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-xylopyranosyl]-5α-cholest-22-ene-3β,6α,8,15β,24-pentol (ceramasteroside C₅)). Three known polyhydroxysteroids (24-methylene-5α-cholestane-3β,6α,8,15β,16β,26-hexol, 5α-cholestane-3β,6α,8,15β,16β,26-hexol, and 5α-cholestane-3β,6β,15α,16β,26-pentol) were also isolated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 1997.     

Steroidal glycosides from Allium cyrillii bulbs

Two spirostanol saponins, one of which was a new compound, were isolated among the steroidal glycosides of Allium cyrillii Ten. Bulbs. The structures of these glycosides were established using chemical and spectral analytical methods as β-D-glycopyranosyl-(1 → 2)-[β-D-xylopyranosyl-(1 → 3)]-β-D-glucopyranosyl-(1 → 4)β-D-galactopyranosyl-(1 → 3)-(25R)-5α-spirostan-2α,3β-diol and β-D-glucopyranosyl-(1 → 2)-[4-O-(3hydroxy-3-methylglutaryl)-β-D-xylopyranosyl-(1 → 3)]-β-D-glucopyranosyl-(1 → 4)-β-D-galactopyranosyl(1 → 3)-(25R)-5α-spirostan-2α,3β-diol.     

Polar steroidal compounds from the Far-Eastern starfish <Emphasis Type="Italic">Lethasterias fusca</Emphasis>

Nine steroidal compounds including three new steroidal glycosides, viz., sodium (24S)-3,24-di-O-(β-D-xylopyranosyl)-5α-cholestane-3β,6β,8,15α,24-pentol 15-sulfate (fuscaside A), (24S)-3,24-di-O-(β-D-xylopyranosyl)-5α-cholestane-3β,6β,8,15α,24-pentol (fuscaside B), and (22E,24R)-24-O-(β-D-xylopyranosyl)-5α-cholest-22-ene-3β,6α,8,15β,24-pentol (desulfated minutoside A); three previously known glycosides, viz., distolasterosides D₁ and D₂ and pycno-podioside A; two previously known polyhydroxysteroids, viz., 5α-cholestane-3β,6α,8,15β,16β,26-hexaol and 5α-cholestan-3β,4β,6α,7⇇8,15β,16β,26-octol; and the known sodium 24,25-dihydro-marthasterone 3-sulfate were isolated from the Far-Eastern starfish Lethasterias fusca. The structures of these compounds were elucidated by NMR spectroscopy and mass spectrometry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 196–200, January, 2008.     

Two-fragment α-adrenolytics

Dialkyl β-(2-aroxyethylamino)ethylphosphonates,N-[β-(2-methoxyphenoxy)ethyl]-N′-[β-(diethoxyphosphoryl)ethyl]-α,ω-diaminoalkanes, and diethyl β-(N-arylpiperazino)ethyl-phosphonates were synthesized by the reactions of dialkyl vinylphosphonates with β-aroxyethylamines,N-[β-(2-methoxyphenoxy)ethyl]-α,ω-diaminoalkanes, andN-aryl-piperazines, respectively. The compounds synthesized exhibit hypotensive and α-adrenolytic activities. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 987–991, May 1999.     

Steroidal glycosides of gitogenin from Allium rotundum

Two new steroidal glycosides were isolated by fractionation of total extracted substances from inflorescences and flower stalks of Allium rotundum (Alliaceae). The structures were determined on the basis of chemical transformations, physical constants, and spectral data as 26-O-β-D-glucopyranosyl-(25R)-5α-furostan2α,3β,22α,26-tetraol 3-O-β-D-glucopyranosyl-(1 → 2)[β-D-xylopyranosyl-(1 → 3)]-β-D-glucopyranosyl(1 → 4)-β-D-galactopyranoside (2) and (25R)-5α-spirostan-2α,3β-diol 3-O-β-D-glucopyranosyl-(1 → 3)-βD-glucopyranosyl-(1 → 2)-[β-D-xylopyranosyl-(1 → 3)]-β-D-glucopyranosyl-(1 → 4)-β-D-galactopyranoside (3).     

Two new triterpenoid saponins from <Emphasis Type="Italic">Lysimachia davurica</Emphasis>

Two new saponins were isolated from an ethanol extract of the whole plants of Lysimachia davuria. The new saponins were respectively characterized as 3-O-{β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-L-arabinopyranosyl}-3β,28-dihydroxyolean-12-en-30-oic acid-O-[β-D-xylopyranosyl-(1→2)-β-D-glucopyranosyl]-ester (1) and 3-O-{ β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-L-arabinopyranosyl}-3β,28-dihydroxyolean-12-en-30-oic acid-O-β-D-glucopyranosyl-ester (2). Their structures were determined by 1D, 2D NMR and MS techniques. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 466–468, September–October, 2007.     

Synthesis,isolation, and purification of benzylpenicillin β-diethylaminoethyl ester hydroiodide

Processes of synthesis, isolation, and purification of benzylpenicillin β-diethylaminoethyl ester hydroiodide were studied. The optimal conditions of benzylpenicillin esterification with chloroethyldiethylamine in dimetylformamide and acetonitrile were found. Processes for isolation of the target product were developed and its physicochemical properties were studied. Product stabilization conditions providing a stable pH value in solutions of benzylpenicillin β-diethylaminoethyl ester hydroiodide were found.     

Special Reactions of α,β-Unsaturated Ketones III [1]. Formation and Structure Elucidation of Dimers of 2-Aryl-methyleneketones: (5E)-5-Benzylidene-9β-phenyl-trans-4a-1,2,3,4,4a,5,6,7,8,9a-decahydroxanthen-4aα-ol and 3β,5β-Bis-(4-methoxyphenyl)-2α,4β,6α-trimethyl-4α-propionyl-cyclohexanone [2]

Summary.  The reaction of 2-benzylidenecyclohexanone and 1-(4-methoxyphenyl)-2-methyl-1-penten-3-one with guanidine did not yield the expected 4-phenylhexahydro-2-quinazolinamine and 4-(p-methoxyphenyl)-dihydro-2-pyrimidinamine, respectively, but nitrogen-free products which turned out as [3+3]- and [4+2]-cycloadducts of two molecules of the applied vinylogous ketone each. According to elemental analyses, mass spectra, and, in particular, NMR analyses (¹H and ¹³CNMR, HH-COSY, gs-HSQC, gs-HMBC, 1D TOCSY, NOESY, and 1D NOE difference spectra), the prepared dimers were identified as racemic (5E)-5-benzylidene-9β-phenyl-trans-4a-1,2,3,4,4a,5,6,7,8,9a-decahydroxanthen-4aα-ol and 3β,5β-bis-(4-methoxyphenyl)-2α,4β,6α-trimethyl-4α- propionylcyclohexanone, respectively. Structure and stereochemistry of the dimers are elucidated, and mechanisms for their formation are proposed. Received April 11, 2001. Accepted (revised) May 18, 2001     

A new furostanol glycoside with fatty acid synthase inhibitory activity from <Emphasis Type="Italic">Ophiopogon japonicusa</Emphasis>

A new furostanol glycoside, named ophiopogonin J (1), was isolated from the fibrous root of Ophiopogon japonicas. The structure of the compound was established as (25R)-26-[(O-β-D-glucopyranosyl-(1 → 2)-β-D-glucopyranosyl)]-20α -hydroxyfurost-5, 22-diene-3-O-α-L-rhamnopyranosyl-(1 → 2)-[β-D-xylopyranosyl(1 → 4)]-β-D-glucopyranoside on the basis of spectroscopic methods, including HR-ESI-MS and 1D and 2D NMR experiments.     

Sulfated steroid glycosides from the Viet Namese starfish <Emphasis Type="Italic">Linckia laevigata</Emphasis>

Five sulfated steriodal compounds including one new glycoside called linckoside L7 (1) and four previously known glycosides 2–5 were isolated from the starfish Linckia laevigata. The structure sodium (22E, 24R)-3-O-(2-O-methyl-β-D-xylopyranosyl)-29-O-(β-D-xylopyranosyl)-24-ethylcholest-4,22-dien-3β,6β,8,15α,16β,29-hexaol 15-O-sulfate was proposed for L7. Linckoside L7 inhibited fertilization and egg-cell development in the sea urchin Strongylocentrotus intermedius. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 64–67, January–February, 2007.     

Evasteriosides A and B and other sulfated steroids from the Pacific starfish <Emphasis Type="Italic">Evasterias retifera</Emphasis>

Two new polar steroidal glycosides identified as sodium (20R,22E,24R,25S)-3-O-(β-d-xylopyranosyl)-24-methyl-5α-cholest-22-ene-3β,6β,8,15α,26-pentol 26-sulfate (evasterioside A) and sodium (20R,22E)-24-O-(β-d-xylopyranosyl)-5α-cholest-22-ene-3β,6β,8,15α,24-pentol 3-sulfate (evasterioside B) were isolated from the Pacific starfish Evasterias retifera collected in the Sea of Japan. Five known compounds, viz., coscinasterioside B, aphelasterioside A, marthasterone 3-sulfate and (20R)-cholest-7-en-3β-ol and cholesterol sulfates, were identified. The structures of the new natural compounds were established using their 2D NMR and mass spectra and some chemical transformations.     

New steroidal glycosides from the stem bark of <Emphasis Type="Italic">Mimusops elengi</Emphasis>

Two new steroidal glycosides (1 and 2) have been isolated from the ethanolic extract of the stem bark of Mimusops elengi L. and characterized as stigmasta-5,22-dien-3β-ol-3β-D-glucuropyranosyl-(6′β→1″)-D-glucopyranoside (1) and β-sitosterol-3β-(3″′,6″′,7″′-trihydroxynaphthyl-2″′-carboxyl)-4″-glucopyranosyl-(1″→4′)-glucopyranoside (2) along with the known compounds stigmasta-5-en-3β-ol, lup-20(29)-en-3β-ol, and stigmasta-5-en-3β-D-glucopyranoside. Their structures have been elucidated on the basis of spectral data analysis and chemical reactions.     

Cardiotonic steroids with additional lactone rings

Stereochemical structural transformations of cardiosteroids to create in them additional lactone rings were studied. Creation of δ-lactones by reaction of a 3β-OH group and a 19-carboxylic group to give the corresponding A/B-trans cardiosteroids and creation of β-lactones by reaction of a 5β-OH group and a 19-COOH to give the corresponding A/B-cis steroids were studied. The new biologically active compounds 8(14)-dehydrobovogenin-19-carboxylic acid 3β-O-19-lactone, strophanthidine-19-carboxylic acid 5β-O-19-lactone, cymarin-19-carboxylic acid 5β-O-19-lactone, convallatoxin-19-carboxylic acid 5β-O-19-lactone, and strophalloside-19-carboxylic acid 5β-O-19-lactone were prepared.     

A step forward in the field of drug design: 1,5-benzothiazepines and their nucleosides

(±)cis-2-(4-methoxyphenyl)-3-hydroxy/methoxy-6-methoxy/8-methoxy-2,3-dihydro-1,5-benzothiazepin-4-[5H/5-chloroacetyl/5-(4′-methylpiperazino-1′)acetyl]-ones and nucleosides viz; (±)cis-2-(4-methoxyphenyl)-3,6-dimethoxy-2,3-dihydro-1,5-benzothiazepin-4-[5-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)]-one and (±)cis-2-(4-methoxyphenyl)-3,8-dimethoxy-2,3-dihydro-1,5-benzothiazepin-4-[5-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)]-one have been synthesized by the condensation of substituted-2-aminobenzenethiols with methyl (±)trans-3-(4-methoxyphenyl)glycidate in xylene and by stirring the 3-methoxy derivative of 1,5-benzothiazepin-4(5H)-ones with sugar namely β-D-ribofuranosyl-1-acetate-2,3,5-tribenzoate at 155–160 °C in vacuo for 10 hours, respectively. The synthesized compounds have been characterized by the elemental analyses and spectral data and screened for their antimicrobial activity.     

New Oligomeric Proanthocyanidins from Bark of <Emphasis Type="Italic">Platanus orientalis</Emphasis>

Two oligomeric proanthocyanidinglycosides were isolated from bark of Platanus orientalis. Their structures and relative configurations were established as 7-O-β-D-Glcp-(−)-epicatechingallate-(4β-8)-(−)-epicatechin-(4β-8)-(−)-epicatechin-(4β-8)-5-O-β-D-Glcp-epicatechingallate (Pl-1) and 7-O-β-D-Glc→6-O-β-D-Glcp-(−)-epigallocatechingallate-(4β-8)-(+)-catechingallate-(4β-8)-(+)-catechingallate-(4β-8)-(−)-epigallocatechingallate-(4α-8)-(−)-epicatechin-(4β-8)-[5-O-β-D-Glcp-→6-O-β-D-Glc→6-galloyl(−)-epigallocatechingallate (Pl-7). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 325–330, July–August, 2005.     

Synthesis of 20<Emphasis Type="Italic">S</Emphasis>-protopanaxadiol <Emphasis Type="Italic">β</Emphasis>-D-galactopyranosides

20S-Protopanaxadiol (3β,12β,20S-trihydroxydammar-24-ene) 3-, 12-, and 20-O-β-D-galactopyranosides were synthesized for the first time. Condensation of 12β-acetoxy-3β,20S-dihydroxydammar-24-ene (1) and 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosylbromide (α-acetobromogalactose) (2) under Koenigs–Knorr conditions with subsequent removal of the protecting groups resulted in regio- and stereoselective formation of 20S-protopanaxadiol 3-O-β-D-galactopyranoside, an analog of the natural ginsenoside Rh₂. Glycosylation of 12β,20S-dihydroxydammar-24-en-3-one (5) by 2 with subsequent treatment of the reaction products with NaBH₄ in isopropanol and deacetylation with NaOMe gave 20S-protopanaxadiol 12- and 20-O-β-Dgalactopyranosides.     

Structure of a steroid saponin from <Emphasis Type="Italic">Digitalis ciliata</Emphasis>

A new steroid glycoside was isolated from leaves of Digitalis ciliata (Scrophulariaceae) by fractionation of the total extracted substances. Its structure was determined as (25R)-5α-spirostan-3β-ol 3-O-β-D-glucopyranosyl-(1→3)[β-D-fucopyranosyl-(1→2)]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside based on chemical transformations, physical constants, and spectral data. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 135–137, March–April, 2007.     

Steroid saponins and sapogenins ofAllium IX. The structure of aginoside

From a methanolic extract of the skins of the bulbs ofAllium giganteum Rgl, a new steroid glycoside has been isolated — aginoside, which is (25R)-5α-spirostan-2α, 3β, 6β-triol 3-0-{[0-β-D-xylopyranosyl-(1→3)-]-[0-β-D-glucopyranosyl-(1→2)]-0-β-D-glucopyranosyl-(1→4)-0-β-D-galactopyranoside}.     

Asterosaponin P2 from the Far-Eastern starfishpatiria (asterina) pectinifera

A new polyhydroxylated steroidal glycoside, asterosaponin P₂, was isolated from the Far-Eastern starfishPatiria (Asterina) pectinifera. The glycoside was identified as the 24R)-29-O-[2-O-sulfo-α-L-arabinofuranosyl]-24-ethyl-5α-cholestane-3β, 6α,8β,15α,16β,29-hexol Na salt. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1818–1820, October. 2000