Showing papers by "Tolstikov Genrikh A published in 2001"
TL;DR: In this article, the use of sulfonium ylides in the synthesis of carbocyclic and hetercyclic compounds is analyzed, systematised and generalised.
Abstract: Data on the use of sulfonium ylides in the synthesis of carbocyclic and heterocyclic compounds published over the last 15 years are analysed, systematised and generalised. The bibliography includes 139 references.
33 citations
TL;DR: Glycyrrhizic acid is a triterpene glycoside representing the main active component of licorice root extract obtained from plants of the GlycyRrhiza glabra L., Glycyr rhiza uralensis Fisher, or Glucyr Rhiza Korshinskyi Grig species.
Abstract: Glycyrrhizic acid (GA, I) is a triterpene glycoside representing the main active component of licorice root extract obtained from plants of the Glycyrrhiza glabra L., Glycyrrhiza uralensis Fisher, or Glucyrrhiza Korshinskyi Grig. species. GA preparations exhibit various types of pharmacological activity, including antiviral [1, 2] and antitumor properties [3, 4]. Small doses of GA stimulate the production of -interferon both in vitro and in vivo [5, 6]. It was also reported that GA and its derivatives are capable of inhibiting HIV and Marburg viruses [7, 8].
28 citations
TL;DR: In this article, a complex formation between chlorine dioxide and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its thermodynamic characteristics were studied in a number of organic solvents.
13 citations
TL;DR: In this article, a series of 3-O-acylates of methyl esters of 18 and 18-glycyrrhetic acids and their 11-deoxoand 18,19-dehydro analogs were synthesized.
Abstract: Typically possessing low toxicity and a broad spectrum of biological activity, plant triterpenoids are valuable raw materials for the creation of new drugs [1 – 4]. Of special interest in this respect are the major triterpenoids contained in the root extract obtained from plants of the common licorice (Glycyrrhiza glabra L.) and Ural licorice (Glycyrrhiza uralensis Fisher ) species. These substances are represented by 18 -glycyrrhetic acid (I) and its modified analogs, which serve as the base for effective antiinflammatory, antiallergic, and antiulcer preparations [2, 5 – 9]. The antiulcer drugs include the sodium salt of acid I (glycyrrhenate sodium) [2] and the disodium salt of acid I succinate (carbenoxolone, II) [6, 7]. In continuation of our previous study devoted to the synthetic transformation of triterpenoids extracted from licorice root [10], we have synthesized a series of 3-O-acylates of methyl esters of 18 and 18 -glycyrrhetic acids and their 11-deoxoand 18,19-dehydro analogs (III – IX).
12 citations
TL;DR: In this article, a series of complex compounds involving acid I and drugs II and V in 1 : 1 ratio were synthesized in a water- ethanol medium at ~50°C.
Abstract: A promising way of creating new highly effective drugs is the synthesis of molecular complexes which can protect parent substances from premature metabolic decay and provide for their controlled release. A premise in our approach was that the complex-forming agent must contain both a hydrophilic component (binding the main parent substance) and a hydrophobic component (responsible for the drug transport). Previously, we demonstrated that the molecular complexes of -glycyrrhizic acid (I) with prostaglandins and nonsteroidal antiinflammatory drugs are characterized by reduced toxicity and increased therapeutic breadth as compared to those of the components [1 – 6]. The main disadvantage of the well-known antitumor drugs 5-fluorouracil (II), ftorafur (III), rubomycin (IV), and their analogs is high toxicity [7 – 9]. We have synthesized a series of complex compounds involving acid I and drugs II – V in 1 : 1 ratio. The molecular complexes of I with fluorouracil were obtained in a water – ethanol medium at ~50°C, and the complexes with anthracycline antibiotics, in ethanol at room temperature. All compounds were characterized by IR and UV spectra. The UV spectra of complexes I II and I III exhibit intense absorption maxima in the region of 250 – 260 nm, related to the total absorption of conjugated ketone and fluoropyrimidine chromophore groups. The UV spectra of complexes I IV and I V display intense maxima in the region characteristic of aromatic chromophores (234 – 235 nm) and new maxima related to anthracycline groups (470 – 530 nm). As can be seen from the data in Table 1, the complexes of I with compounds II – IV are less toxic than the initial antitumor drugs. According to the results of preliminary experiments, the molecular complex of acid I with drug III exhibits antitumor action with respect to Pliss lymphosarcoma, melanoma B-16, and Guerin’s carcinoma (Table 2).
12 citations
TL;DR: A procedure for direct reduction of peroxide products resulting from ozonolysis of 1-methylcycloalkenes to the corresponding hydroxyketones by the action of sodium triacetoxohydridoborate was proposed in this article.
Abstract: A procedure was proposed for direct reduction of peroxide products resulting from ozonolysis of 1-methylcycloalkenes to the corresponding hydroxyketones by the action of sodium triacetoxohydridoborate.
10 citations
TL;DR: New potential juvenoids, esters of alkenoic and alkadienoic acids with phenoxy-and phenoxyphenoxyethanol were synthesized as mentioned in this paper.
Abstract: New potential juvenoids, esters of alkenoic and alkadienoic acids with phenoxy- and phenoxyphenoxyethanol were synthesized, and also esters of phenoxyacetic acid with alkenols amd alkadienols.
9 citations
TL;DR: In this paper, a one-pot catalytic method for the synthesis of 1,1-disubstituted cyclopropanes starting from olefins, acetylenes and AlEt3 in the presence of Cp2ZrCl2, via a step involving in situ formation of aluminacyclopentanes and aluminates, respectively, was developed.
9 citations
TL;DR: Petrov and Sapozhnikova as discussed by the authors showed that 3-thiabis(cyclohexanecarboxylic) acid derivatives possess a more or less pronounced antiinflammatory activity.
Abstract: The class of antiinflammatory drugs includes a group of sulfur-containing organic compounds such as metiazinic acid, tinoridine (kenfamin), tiaramide (solantol), etc. However, all these drugs give rise to side effects, including gastrointestinal tract disorders. A pronounced antiinflammatory activity was reported for patented cyclic hydroxysulfones [1], the most active of which was 3-hydroxytetrahydrothiophene-1,1-dioxide (3-hydroxysulfolan). The results of investigations carried out in the Laboratory of New Drugs at the Institute of Organic Chemistry (Ufa) showed that most of the synthetic sulfones possess a more or less pronounced antiinflammatory activity. The maximum activity was observed for dihydroxysulfolan, producing, in contrast to most of the known antiinflammatory sulfur-containing compounds, no ulcerogenic action. The purpose of this work was to synthesize and characterize a series of new 3-thiabis(cyclohexanecarboxylic) acid derivatives. The condensation of piperylene (Ia) with acrylic acid nitrile (II) was conducted by the method described in [2 – 4] to obtain 2-methyl-1,2,5,6-tetrahydrobenzonitrile (IIIa) with a yield of 90%. As was previously established by A. A. Petrov and A. F. Sapozhnikova for an initial mixture containing cis and trans forms of piperylene in a 50 : 50 ratio, the condensation with acrylonitrile at 130 – 135°C involves only the trans form, whereas the cis form does not enter the reaction at this temperature. However, a complete condensation takes place at 180°C, when the cis to trans conversion obviously takes place. We conducted the condensation process with a cis– trans mixture for 12 h at 140°C; the unreacted cis-piperylene was distilled off. The synthesis was conducted according to the following scheme. I – V: R = Me (a), H (b); VI: R = Me (a – c), H (d); R = C4H8NO (a, b, d), C5H10N (c); X = H (a), Na (b – d).
8 citations
TL;DR: In this paper, the results of diterpene alkaloids by dimethyldioxirane were studied with eldeline, talatizamine, aconitine, and zongorine as examples.
Abstract: Oxidation of diterpene alkaloids by dimethyldioxirane was studied with eldeline, talatizamine, aconitine, and zongorine as examples. Nitrones and 19-oxo derivatives of bases were obtained. The results of the oxidation allow one to draw an analogy with the oxidation by KMnO4 and to suggest a mechanism of the reaction.
8 citations
TL;DR: In this paper, the crystal and molecular structure of the Z-isomer was established by X-ray diffraction analysis and its structure was also confirmed by the spectral data (2D 1H, 1H and 13C, NMR spectroscopy and mass spectrometry).
Abstract: Oximation of songorine afforded a mixture of its Z- and E-oximes. The crystal and molecular structure of the Z-isomer was established by X-ray diffraction analysis. Its structure was also confirmed by the spectral data (2D 1H—1H and 13C—1H NMR spectroscopy and mass spectrometry). The structure of isomeric E-oxime was established by comparing its NMR spectroscopic data (1H and 13C) with the data for the Z-isomer.
TL;DR: In this article, the configuration of the C(17) asymmetric center in 15-O-deacetylrhaposerin was established by X-ray diffraction analysis and the molecular structure of rhaserin was determined based on the data from 1H and 13C NMR spectroscopy.
Abstract: As part of our continuing studies of lactones from the aerial part of the plant Rhaponticum serratuloides, 15-O-deacetylrhaposerin and new guaianolide called rhaserin were isolated along with the well-known loliolide. The configuration of the C(17) asymmetric center in 15-O-deacetylrhaposerin was established by X-ray diffraction analysis. The molecular structure of rhaserin was determined based on the data from 1H and 13C NMR spectroscopy (including 2D NMR spectroscopy) of this lactone and its 4,15-O-isopropylidene derivative.
TL;DR: This work has proposed a method of obtaining purified glycyrrhizic acid (84 – 89%) from a commercial dry licorice root extract containing 26 – 28% of glycosides (available from the Urals Licorice Plant).
Abstract: Glycyrrhizic acid (I) is an active component of licorice root extract obtained from plants of the Glycyrrhiza glabra L. and Glycyrrhiza uralensis Fisher species. The derivatives of acid I possess a broad spectrum of pharmacological properties, including antiinflammatory, antiulcer, antiallergic, antidote, antiviral, and some other types of activity [1]. Glycyrrhizic acid and its salts were recommended for the treatment of various forms of skin and liver cancer [2, 3] and are successfully used in the form of Stronger Neo-Minophagen C (SNMC) preparation for the therapy of patients with AIDS and hepatitis B [4, 5]. A purified glycoside component enters into the drug Clatraprostin (a veterinary preparation) and is used in the new medicinal forms of nonsteroidal antiinflammatory drugs and some other preparations [6, 7]. Previously [8] we proposed a method of obtaining purified glycyrrhizic acid (84 – 89%) from a commercial dry licorice root extract containing 26 – 28% of glycosides (available from the Urals Licorice Plant). Another commercial raw material that can be used for the synthesis of glycyrrhizic acid is glycyrram – a monoammonium salt of glycyrrhizic acid (available from the Chimkentbiofarm corporation). Glycyrram is an antiinflammatory drug used for the treatment of bronchial asthma, eczemas, and allergic dermatitis [9]. For the synthesis of pure glycyrrhizic acid from a commercial monoammonium salt, Volan and Dumazert [10] recrystallized the commercial product from acetic acid (AcOH) and ethanol, after which the purified glycoside was converted into a tripotassium salt (3K-salt) (II). Finally, salt II was converted into glycyrrhizic acid by acidification with an aqueous H 2 SO 4 solution. I: R = R = H, II: R = R = K, III: R = K, R = H.
TL;DR: In this article, 13-hydroxy-2-oxotridecane is synthesized via ozonolysis of 1-methylcyclododecene and tetradec-13-en-2 -one, the product from mono-alkylation of the acetoacetic ester with 1-bromo-10-undecene followed bydecarbethoxylation, with further reduction of the intermediate peroxides using NaBH(OAc)(3)
Abstract: 13-Hydroxy-2-oxotridecane, which is isolated from extract ofEvodia hupehensisDode honey-bee eggs and actively attracts honey bees, is synthesized via ozonolysis of 1-methylcyclododecene and tetradec-13-en-2-one, the product from monoalkylation of the acetoacetic ester with 1-bromo-10-undecene followed bydecarbethoxylation, with further reduction of the intermediate peroxides using NaBH(OAc)
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TL;DR: The formation of charge transfer complexes between chlorine dioxide and nitroxyl radicals (2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2, 2, 6, 6-6-TTE-triggered) in acetone, acetonitrile, n-heptane, diethyl ether, carbon tetrachloride, toluene, and dichloromethane was found by spectrophotometry at +20°C as mentioned in this paper.
Abstract: The formation of charge transfer complexes between chlorine dioxide and nitroxyl radicals (2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-acetylamido-2,2,6,6-tetramethylpiperidin-1-oxyl, 2,2,5,5-tetramethyl-4-phenyl-3-imidazolin-1-oxyl, and bis(4-methoxyphenyl) nitroxide) in acetone, acetonitrile, n-heptane, diethyl ether, carbon tetrachloride, toluene, and dichloromethane was found by spectrophotometry at –60—+20 °C The thermodynamic parameters of complex formation were determined The radical structure affects its complex formation ability The charge transfer complex is transformed into the corresponding oxoammonium salt
TL;DR: The ability of Rhodococcus bacteria to transform dehydroabietic and isopimaric acids with a high degree of conversion (up to 95%) was detected as mentioned in this paper.
TL;DR: In this article, the ozonolysis of isoabienol in MeOH followed by hydrogenation of the peroxide ozonizing products on Lindlar catalyst afforded ambreinolide that under treatment with diisobutylaluminum hydride furnished 8α,13-epoxy-14,15,16-trisnorlabd-12-ene.
Abstract: The ozonolysis of isoabienol in MeOH followed by hydrogenation of the peroxide ozonolysis products on Lindlar catalyst afforded ambreinolide that under treatment with diisobutylaluminum hydride furnished 8α,13-epoxy-14,15,16-trisnorlabd-12-ene.
TL;DR: Oktyabrya and Vorozhtsov as mentioned in this paper proposed a method for the extraction of organic molecules from organic molecules using the so-called Soedinenii method, which is based on the concept of Soedinenskiy's method.
Abstract: 1) Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, 450054, Ufa, pr. Oktyabrya, 71, fax: (3472) 35 60 66, e-mail: chemorg@anrb.ru; 2) N. N. Vorozhtsov Novosibirsk Ins titute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, 630090, N ovosibirsk, pr. Lavrent 1eva, 9, fax: (3832) 34 47 52, e-mail: gtolstik@nioch.nsc.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 417-418, September-October, 2001. Original article submitted August 1, 2001.
TL;DR: In this paper, 1.7-Hydroxy-5-(2-methoxyphenyl)-2-methyl-6-R-1,4-naphthoquinones, 8-hydroxy-1-(2.m.oxymethyl)-3-oxo,1,2,3, 4-tetrahydro-9,10-anthraquinone, and 2.
Abstract: 7-Hydroxy-5-(2-methoxyphenyl)-2-methyl-6-R-1,4-naphthoquinones, 8-hydroxy-1-(2-methoxyphenyl)-3-oxo-1,2,3,4-tetrahydro-9,10-anthraquinone, and 2-ethoxycarbonyl-8-hydroxy-1-(2-methoxyphenyl)-3-trimethylsiloxy-1,1a,4,4a-tetrahydro-9,10-anthraquinone were synthesized by reactions of 1-(2-methoxyphenyl)-2-R-3-trimethylsiloxy-1,3-butadienes with 2-bromo-5-methyl-1,4-benzoquinone and juglone. 1-Aryl-2-ethoxycarbonyl-3-trimethylsiloxy-1,3-butadienes reacted with 1,4-naphthoquinone to afford 1-aryl-2-ethoxycarbonyl-3-hydroxy-9,10-anthraquinones and their 4,4a-dihydro derivatives.
TL;DR: In this paper, a scheme of ketocaronic acid formation was suggested based on kinetics of ozone reaction with 3-caren-5-one and thermal decomposition of peroxides.
Abstract: Cleavage by ozonolysis of a cyclic unsaturated ketone, 3-caren-5-one, was investigated under different conditions. The main reaction product is ketocaronic acid. A scheme of ketocaronic acid formation was suggested basing on kinetics of ozone reaction with 3-caren-5-one and thermal decomposition of peroxides.
TL;DR: In this article, the initial compounds were 1,3-bis(2-hydroxy-3-chloropropyl)-6-methyluracil (I, synthesized from uracil and epichlorohydrin) and 1, 3-bis-2-hexylhexyl hexoxide (hexoxyhexoxide) 6-methylURACil (II) by substituting radicals for chlorine by reactions with secondary amines.
Abstract: The initial compounds were 1,3-bis(2-hydroxy-3-chloropropyl)uracil (I, synthesized from uracil and epichlorohydrin) and 1,3-bis(2-hydroxy-3-chloropropyl)-6-methyluracil (II). Upon substituting radicals for chlorine in compounds I and II by reactions with secondary amines, we obtained compounds III – X. Alternatively, compounds IV and VI can be obtained by treating methyluracil II with a fourfold excess of morpholine or piperidine at 120 – 150°C [5]. However, the latter method failed to yield pure acyclonucleosides with dimethylamine and diethylamine substituents because these products (well soluble in water) were difficult to isolate. These substituents were successfully synthesized upon changing the process conditions: we employed methyl alcohol as the solvent and conducted the reaction for 1.5 – 3 h at 20 – 60°C in the presence of K2CO3. The proposed structures of the synthesized compounds were confirmed by elemental analyses and by the data of IR, UV, and NMR (H and C) spectroscopy. The IR spectra of all compounds display absorption bands in the region of 1620 – 1720 cm – 1 characteristic of the stretching vibrations CO and =N–C=O of the pyrimidine fragment. The spectra of compounds I and II exhibit the characteristic absorption bands in the regions of 500 – 840 cm – 1 ( CCl) and 1280 – 1290 cm – 1 ( CH Cl 2 ). Absorption bands at 1060 – 1240 cm – 1 are indicative of a tertiary nitrogen atom, and the bands at 3300 – 3500 cm – 1 are due to the stretching vibrations of OH and NH bonds. In the spectra of compounds I, III, V, VII, and IX, the front of the latter band was displaced to 3400 cm – , probably, because the hydroxy group at C participated in a hydrogen bond formation. The C NMR spectra of all compounds exhibited well-known signals due to carbons of the uracil fragment. However, the signals from C in the spectra of compounds I, III, V, VII, and IX were shifted to 102.87 ppm. Apparently, all compounds are featuring a strong hydrogen bond between the hydroxy groups of C and the keto group. This results in a significant difference between C NMR signals from carbons of the substituents at N and N, while the signals from C and C shift toward stronger fields: in the absence of hydrogen bonding, the chemical shift of the signal from C must take a theoretical value of about 125.42 ppm. The H NMR spectra display the signals from protons at C and C of the
TL;DR: The known norditerpenoid alkaloid mesaconitine and a new alkalinoid acsonine 1 were isolated from the roots of Aconitum kusnezoffii Reichb as discussed by the authors.
Abstract: The known norditerpenoid alkaloid mesaconitine and a new alkaloid acsonine 1 were isolated from the roots of Aconitum kusnezoffii Reichb. The structure of 1 was established based on spectroscopic data.
TL;DR: A promising approach to searching for new biologically active agents is synthesis of combined compounds whose molecules consist of the structural elements of pharmacons with a known activity and natural bioregulators (e.g., those of plant origin).
Abstract: Intellectual and memory impairment is known to be a common complication of functional disorders of the central nervous system, neuropsychic, and neurological diseases. Therefore, the search for neurotropic agents with complex effects, including the nootropic effect, is topical [1, 2]. During our studies on purpose-oriented bioscreening of substances of plant origin, we showed that methyl lambertianate (Me-LA, I), a component of the Siberian cedar ( Pinus sibirica R. Mayr.) needles, exerted a marked nootropic effect. This is a new type of biological activity of terpenoids of the labdan series. Earlier, we found a psychotropic action of Me-LA (I) [3]. In our opinion, a promising approach to searching for new biologically active agents is synthesis of combined compounds whose molecules consist of the structural elements of pharmacons with a known activity and natural bioregulators (e.g., those of plant origin). Therefore, we synthesized a GABA-derivative of methyl lambertianate (II) and found an increased anxiolytic effect.
TL;DR: In this paper, the first elatidam and elatidal were obtained by oxidation of the diterpene alkaloid elatidine with KMnO4 or CrO3 and characterized.
Abstract: Elatidam, elatidamic acid, and elatidal were obtained for the first time by oxidation of the diterpene alkaloid elatidine with KMnO4 or CrO3 and characterized. The reactions of elatidal with hydroxylamine, aniline, allylamine, and methyl glycinate afford the corresponding imines. Elatidal N-phenyl- and N-allylimines were reduced with NaBH4 to give the corresponding diamines.
TL;DR: Condensation of 2-[(E)-pent-3-en-2-yl]-4, 2]-pent-1-enyl]-6-methylaniline with 1-chloro-1-(N-methylimino)- or 1-chloro- 1-(Nphenylimino)ethane affords the corresponding amidines as discussed by the authors.
Abstract: Condensation of 2-[(E)-pent-3-en-2-yl]-4-, 2-[(E)-pent-2-en-2-yl]-4-, or 2-(cyclopent-1-enyl)-6-methylaniline with 1-chloro-1-(N-methylimino)- or 1-chloro-1-(N-phenylimino)ethane affords the corresponding amidines. Cyclization of the N-methylimino derivatives in polyphosphoric acid gives 3,4-dihydroquinazolines in high yields.