Six new withanolide-type steroids from the leaves of Solanum cilistum

Six new withanolide-type steroids, designated cilistols v, t, i, j, y and w (1-6, respectively), were obtained from the leaves of Solanum cilistum. Their respective structures were characterized by spectroscopic means as follows: Cilistol v (1) was (22R,24Z)-1alpha,3beta,22,26-tetrahydroxyergost-5,24-diene 26-O-beta-D-glucopyranoside, which is regarded as the precursor of other withanolide-type steroids included in this title plant. Cilistol t (2) was (22R,24S,25R,26S)-24,25;22,26-diepoxy-1alpha,3beta,26-trihydroxyergost-5-ene 26-O-beta-D-glucopyranoside, and cilistols j (3) and i (4) corresponded to the substances probably formed by the cleavage of the epoxy ring at C-24 and 25 of 2. Cilistol y (5) was 3-O-sulphonyl (22R,24S,25R,26R)-1-oxo-24,25; 22,26-diepoxy-3beta,17alpha,26-trihydroxyergost-5-ene 26-O-beta-D-glucopyranoside, and cilistol w (6) corresponded to the substance obtained by the fission of the epoxy ring at C-24 and 25 of 5. The occurrence of these withanolide type steroids from Solanum genera is rare and worthy of note.     

Four new cycloartane glycosides from Thalictrum fortunei

Four new cycloartane glycosides were isolated from the aerial parts of Thalictrum fortunei (Ranunculaceae). The chemical structures of these new glycosides were elucidated as 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-beta-D-glucopyranoside, 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-beta-D-quinovopyranosyl-(1-->6)-beta-D-glucopyranoside, 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-beta-D-xylopyranosyl-(1-->6)-beta-D-glucopyranoside, and 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranoside by extensive NMR methods, HR-ESI-MS, and hydrolysis. This is the first report of (22S,24Z)-3beta,22,26-trihydroxycycloartan-24-ene (thelictogenin A, 5) being glycosylated at C-26.     

Withasteroids of Physalis. X. Circular dichroism of withasteroids from plants of the genus Physalis

The circular dichroism method has been used to establish the stereochemical features of the structure of the withasteroids. The 22S-configuration of the asymmetric center has been confirmed for physangulide. The 22R-configuration has been confirmed for 14α-hydroxyixocarpanolide, vamonolide, ixocarpanolide, 24,25-epoxywithanolide D, and withanolide T. On the basis of changes in the circular dichroism spectra in acid and alkaline media it is suggested that in compounds having a 4β-hydroxy-1-oxo-5β,6β-epoxy-2,3-ene grouping the Δ^2,3 bond disappears, while in compounds having a 5α-hydroxy-1-oxo-6α,7α-epoxy-2,3-ene grouping dehydration takes place at C-4-C-5. These characteristics can be used in the identification of the withasteroids. The isolation of withanolide T from the leaves ofPhysalis angulata L. is described and its spectral characteristics are given. Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 371–376, May–June, 1990.     

A novel synthesis for quinoline derivatives

Condensation of ethyl 2-(2-oxo-2,3-dihydro-1H-indolid-3-ene)cyanoacetate and/or 2-(2-oxo-2,3-dihydro-1H-indolid-2-ene)malononitrile with 3-methylpyrazolin-5-one, 1-phenyl-3-methyl-pyrazolin-5-one, benzoyl acetonitrile or ethyl acetoacetate affords different substituted quinolines. The reaction is suggested to proceed through a nucleophilic addition followed by ring opening and recyclization steps.     

Steroidal alkaloids from the bulbs of Fritillaria monatha

Two new Steroidal alkaloids, named pengbeisine A and pengbeisine B, were isolated from the fresh bulbs of Fritillaria monatha Migo. along with a known alkaloid. The structures were characterized as 22,26-imino-17, 23-oxido-5α-jerv-6-oxo-2α,3β-diol and 22, 26-imino-17, 23-oxido-5α-jerv-6-oxo-2β,3α-diol on the basis of spectroscopic methods.     

Synthesis of some substituted 1,3-thiazolines and 1,3-thiazolidines

Sodium salts of 2, 2-dimethyl-4-mercapto-5-oxo-1,3-thiazoline and 2-oxo-3-mercapto-1-thia-4-azaspiro[4.5]dec-3-ene, obtained from a solvate of sodium cyanodithioformate with three molecules of dimethylformamide, acetone, or cyclohexanone in the presence of morpholine, react with chlorothioformic dimethylamide with the formation of 2,2-dimethyl-5-oxo-4-(dimethylaminothiocarbonylthio)-1,3-thiazoline and 2-oxo-3-(dimethylaminothiocarbonylthio)-1-thia-4-azaspiro[4.5]dec-3-ene, respectively, and during acidolysis by hydrochloric acid they are converted to 2,2-dimethyl-5-oxo-4-thiono-1,3-thiazolidine and 2-oxo-3-thiono-1-thia-4-azaspiro[4.5]decane. The latter compounds are facilely phosphorylated by dialkyl chlorophosphonates at the nitrogen atom. The reaction of the solvate of sodium cyanodithioformate with three molecules of dimethylformamide with chloroacetone in the presence of morpho-line occurs anomalously with the formation of cyanothioformic morpholide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2590–2593, November, 1990.     

The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene

The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene gives 6-amino-1,3-dibutyl-5-cyano-2-ethoxy-4-(1-imino-2-cyanoethyl)-2-oxo-1,3,2-diazaphosphindane.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 303–305, February, 1994.     

Synthesis of 1,5-methano-2-benzazocines from 3-hydroxy-1,3-dimethyl-6-phenyl-4-piperidone

Reaction of 3e-hydroxy-1e,3a-dimethyl-6e-phenyl-4-piperidone with cyanoacetic ester affords 6e,8a-dimethyl-2-oxo-5e-phenyl-3-cyanofuro[2,3-c]piperidine, the epoxide of which undergoes intramolecular cyclization on treatment with 80% H₂SO₄, to give 1,2,5,6-tetrahydro-2-endo-4-dimethyl-1,5-methano-6-oxo-2-benzazocin-3-ene. It has been found that the latter is formed via the intermediate 3-hydroxy-6e,8a-dimethyl-2-oxo-5e-phenylfuro[2,3-c]piperidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1371–1374, October, 1986.     

Metabolism of 32-oxo-24,25-dihydrolanosterols by partially purified cytochrome P-450(14DM) from rat liver microsomes

Metabolism of 32-oxo-24,25-dihydrolanosterols (3 beta-hydroxylanost-8-en-32- al (4,delta 8-CHO) and 3 beta-hydroxylanost-7-en-32-al (5,delta 7-CHO)) was studied in a reconstituted system consisting of rat liver partially purified cytochrome P-450, which catalyzes lanosterol 14-demethylation (P-450(14DM)), and reduced nicotineamide adenine dinucleotide phosphate (NADPH)-cytochrome P-450 reductase. The reconstituted system converted delta 8-CHO to 4,4-dimethyl-5 alpha-cholesta-8,14-dien-3 beta-ol (2, 8, 14-Diene), which corresponds to the 14-deformylated product. delta 7-CHO, the isomer of delta 8-CHO, was not converted to the corresponding 14-deformylated product. The apparent Km value of cytochrome P-450(14DM) for delta 8-CHO was about 1/20 of that for 24,25-dihydrolanosterol (1, DHL). The metabolism of delta 8-CHO was inhibited by 7-oxo-24,25-dihydrolanosterol (6, 7-oxo-DHL), which is a potent inhibitor of cholesterol biosynthesis from lanosterol or DHL. However, the metabolism of delta 8-CHO was less inhibited by 7-oxo-DHL than that of DHL.     

Synthesis of 10-Hydroxy- and 9-Oxo-2e-Decenoic Acids from Oleic Acid

A practical synthesis of biologically active 10-hydroxy- and 9-oxo-2E-decenoic acids, components of mandibular gland secretion of honeybee (Apis mellifera L.), is developed using ozonolysis-reduction of oleic acid and 1,9-diacetoxynon-1-ene in the key steps.     

Withasteroids ofPhysalis. VII. 14α-Hydroxyixocarpanolide and 24,25-expoxywithanolide D

Two new withasteroid have been isolated fromPhysalis angulata L. — 14α-hydroxyixocarpanolide and 24,25-epoxywithanolide D. 14α-hydroxyixocarpanolide — C₂₈H₄₀O₇, mp 245–250°C (from methanol), [α] _D ²⁰ +29±2° (chloroform). 24,25-Epoxywithanolide D — C₂₈H₃₈O₇, mp 257–261°C (from methanol, [α] _D ²⁰ +23±2° (chloroform). On the basis of its UV, IR, CD, mass, and¹H and¹³C NMR spectra the structure of 5α,14α,20R-trihydroxy-1-oxo-6α,7α-epoxy-22R-2itha-2-enolide is suggested for 14α-hydroxyixocarpanolide. On the basis of spectral characteristics and the preparation of 4β-acetoxy and 4-oxo derivatives of 24,25-epoxywithanolide D, the structure of 4β,20R-dihydroxy-1-oxo-5β,6β;24S,25S-diepoxy-22R-witha-2-enolide is proposed for it.     

Reaction of grayanotoxin-II with thallium (III) nitrate

Reaction of grayanotoxin-II (1) with thallium nitrate gave 3(S), 20-epoxy-6 (S), 14 (R), 16 (R)-trihydroxy-5-oxo-5, 10-seco-ent-kaur-1 (10) -ene (2). The structure of 2 was elucidated by the X-ray diffraction analysis of its reduction product (3).     

Prostaglandin synthesis from a fulvene with the ω-side chain equivalent

The acid-catalyzed hydrolysis of the Diels-Alder adduct of 6-(2,2-ethylene-dioxyheptyl) fulvene with 2-chloroacrylonitrile gave 7-anti-(3-oxo-1-trans-octenyl)-2-chloro-2-cyanobicyclo[2.2.1]hept-5-ene, which is an intermediate of 12-epi-prostaglandine. On the other hand, the hydrolysis of 7-(3,3-ethylenedioxyoctylidene)bicyclo-[2.2.1]hept-5-en-2-one, obtained from the Diels-Alder adduct of the fulvene with 2-chloroacryloyl chloride, gave a mixture (3:2) of 7-anti- and 7-syn-(3-oxo-1-trans-octenyl)bicyclo[2.2.1]hept-5-en-2-one. The latter compound was oonverted into prostaglandin F_2α.     

Four novel withanolide-type steroids from the leaves of Solanum cilistum.

Four novel withanolide-type steroids named cilistols p, pm, p1 and u (1-4, respectively), were isolated from the leaves of Solanum cilistum. The respective structures were characterized by spectroscopic means as follows: cilistol p (1) was (22R,24R,25R,26S)-1-oxo-22,26-epoxy-3alpha,5alpha-cycloergostane-6beta,17alpha, 24,25,26-pentaol 26-O-beta-D-glucopyranoside, cilistol pm (2) corresponded to the 6-O-methyl ether derivative of 1; cilistol p1 (3) was represented as the 24-O-methyl ether of 1, and cilistol u (4) was shown to be the epoxide between C-24 and -25, presumably bearing cilistols p, pm and p1 by ring-opening.     

Syntheses on the basis of 2H-chromen-2-one and 2H-chromene-2-thione

4-Hydroxy-2H-chromen-2-one and 4-hydroxy-2H-chromene-2-thione reacted with allyl bromide, 1,1,3-trichloroprop-1-ene, and 1,3-dichlorobut-2-ene to give the corresponding ethers, which were oxidized to (2-oxo-2H-chromen-4-yloxy)acetic acid with potassium permanganate, and various derivatives of that acid were obtained. 3-(3,3-Dichloroprop-2-enyl)-7-hydroxy-4-methyl-2H-chromen-2-one and 3-(3,3-dichloroprop-2-enyl)-7-hydroxy-4-methyl-2H-chromene-2-thione were synthesized, and some their transformations were studied.     

Structural analysis of complex saponins of Balanites aegyptiaca by 800 MHz 1H NMR spectroscopy

The main saponin (1) present in the mesocarp of Balanites aegyptiaca fruit is a mixture of 22R and 22S epimers of 26-(O-beta-D-glucopyranosyl)-3-beta-[4-O-(beta-D-glucopyranosyl)-2-O-(alpha-L-rhamnopyranosyl)-beta-D-glucopyranosyloxy]-22,26-dihydroxyfurost-5-ene. This structure differs from a previously reported saponin isolated from this source by the site of attachment of the rhamnosyl residue, and presumably represents a structural revision of the latter. The main saponin (2) present in the kernel is a xylopyranosyl derivative of 1. The use of high-field NMR enabled the practically complete assignment of 1H and 13C chemical shifts of these complex saponins, existing as a mixture of C-22 epimers. Moreover, the work represents a new approach to structural elucidation of saponins: direct preparative-scale HPLC-RID of crude extracts followed by high-field NMR investigations supported by ESI-MSn.     

Synthesis and some properties of 2,2,2-trimethoxy-3-isopropyl-4-bromo-5-oxo-1, 5,2 -oxazaphosphol-4-ene

Conclusions 2,2,2-Trimethoxy-3-isopropyl-4-bromo-5-oxo-1,5,2-oxazaphosphol-4-ene was isolated when trimethyl phosphite is reacted with 1-bromo-1-nitro-3-methyl-1-butene, and some of its transformations were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 462–465, February, 1978.The authors wish to thank É. I. Gol'dfarb for taking the³¹P-¹H} NMDR spectra.     

Synthesis of glutarimide antibiotics and their analogs through 1,3-cycloaddition of 3-glutarimidylacetonitrile oxide to 2-cyclohexenones

A mixture of 4,4-dimethyl-9-(3-methylglutarlmidyl)-2-oxo-7-oxa-8-azabicyclo[4.3.0] non-8-ene and 3-(3-methylglutarimidyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydrobenz-[d]isoxazole was obtained by in situ 1,3-dipolar cycloaddition of 3-glutarimidyl-acetonitrile oxide to 5,5-dimethylcyclohex-2-en-1-one. Reductive cleavage of these compounds by catalytic hydrogenation over Pd catalysts gives 3-[2-amino-2,2-(4,4-dimethyl-2-oxocyclohexylene)ethyl]glutarimide and the known 3-[2-amino-2,2-(4,4-dimethyl-2,6-dioxocyclohexylene)ethyl]glutarimide, respectively, in quantitative yield. Hydrolysis of the latter leads to 3-[2-oxo-2-(4,4-dimethyl-2,6-dioxocyclo-hexyl)ethyl]glutarimide. The ketones obtained are analogs of glutarimide antibiotics and polyfunctional intermediates in their synthesis.See [1] for a preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 230–234, February, 1979.     

Novel transformations of two kinds of chlorinated photo [2 + 2] cycloadducts of 2-pyrone-5-carboxylate

Novel reactions of 7,7-dichloro- and 7,7,8-trichloro-3-oxo-2-oxabicyclo[4.2.0]oct-4-ene-6-carboxylates 5 with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in alcohol gave pyrano[4,3-b]pyran-2,5-diones 8 via (Z)-(2H-pyran-2-on-3-yl)butenoates 7. On the other hand, the same treatment of 7,7,8-trichloro-2-oxo-3-oxabicyclo-[4.2.0]oct-4-ene-5-carboxylate 6b afforded 2-oxo-3-oxabicyclo[4.2.0]oct-4,7-diene-5-carboxylate 14 via cyclobutene formation and S_N2′ displacement by attack of the alkoxy anion.     

Photocycloaddition of 2-Cyanocycloalk-2-Enones to 2, 3-Dimethylbut-2-Ene

Irradiation of 5,5-dimethyl-6-oxocyclohex- l-ene- l-carbonitrile ( 1 ) in the presence of 2,3-dimethylbut-2-ene afforded 3,3,4,4,7,7-hexamethyl-3,4,4a,5,6,7-hexahydroindeno[1,7-c,d]-],2-oxazole (3) in nearly quantitative yield. In contrast, 4,4-dimethyl-5-oxo-cyclopent-l-ene-l-carbonitrile ( 2 ) under the same conditions reacted not to a tricyclic isoxazole but to a 2:1 mixture of 3,3,6,6,7,7-hexamethyl-2-oxo-bicyclo[3.2.0]heptane-l-carbonitrile ( 4 ) and trans-3,3-dimethyl-2-oxo-5-(2,3-dimethylbut-3-en-2-yl)cyclopentane-l-carbonitrile ( 5 ), respectively.