Synthesis of 10-(N′-phenyl)imidoyl derivatives of phenothiazine,and their reactions with o,o-dialkylthio- and dithiophosphates

Condensation of phenothiazine with phenyl isocyanide dichloride has given 10(N-phenylchloroformimidoyl)phenothiazine, exchange reactions of which with salts of diakylthio- and dithiophosphoric acids result in rearrangement of the initially formed 10-[N-phenyldialkoxy(thio)phosphorylthioformimidoyl]phenothiazines to 10-{N-phenyl-N-[dialkoxy(thio)phosphoryl]thiocarbamoyl}phenothiazines, while reaction with diisopropyl dithiophosphoric acid affords diisopropyl chlorothiophosphate, phenyl isothiocyanate, and phenothiazine. 10-(N-Phenylethoxyformimidoyl)phenothiazine alkylates dithiophosphoric acid to give 10-(N-phenylcarbamoyl)phenothiazine, while N²-phenyl-N¹,N¹-diethyl-(10-phenothiazinyl)formamidine reacts with diisopropyl dithiophosphoric acid, affording the salt N²-phenyl-N¹,N¹-diethyl-(10-phenothiazinyl)formamidinium O,O-diisopropyl dithiophosphate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2596–2601, November, 1989.     

Study of furan compounds

Research on synthesis of polycyclic spirans of the 1, 6-dioxaspiro-[4, 4]nonane group is continued. Electrolysis of methanol solutions of 2-furylcyclopentanol, 2-(5-methyl-furfuryl)cyclopentanol, and 2-furfuryl-1-indanol, gives, by intramolecular alkoxylation, spiro{perhydrocyclopenta[b]furan-2, 2-(5dihydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-(5-methoxy-5-methyl-2, 5-dihydrofuran)}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxy-2, 5-dihydrofuran)}, hitherto undescribed in the literature. Depending on the conditions, catalytic hydrogenation of these gives: spiro{perhydiocyclopenta[b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{2, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-tetrahydrofuran}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-tetrahydrofuran}.For Part XXXI see [1].     

1-Aryl-6-azauracile, 5. Mitt.: Die Synthese von 1-(β-Pyridyl)-6-azauracil-5-carbonsäure und einiger ihrer Derivate

Zusammenfassung Analog wie in vorherigen Mitteilungen^1–4 wurden -Pyridyl-hydrazono-cyanacetylcarbamidsäureäthylester (1), 1-(-Pyridyl)-5-cyan-6-azauracil (2), 1-(-Pyridyl)-6-azauracil-5-carbonsäure (3), deren Thioamid (4), und Amidoxim (5), welches in 1-(-Pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6) überge-führt wurde, hergestellt.

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-Pyridylhydrazono-cyanacetylcarbamic acid ethyl ester (1), l-(-pyridyl)-5-cyano-6-azauracil (2), 1-(-pyridyl)-6-azauracil-5-carboxylic acid (3), its thioamide (4) and amidoxime (5) were prepared as described in preceding communications. (5) was converted into l-(-pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6).

     

New terpenoid coumarins from Ferula tadshikorum

Summary Two new terpenoid coumarins — tadzhiferin (I) and tadzhikorin (II) — have been isolated from the fruit ofFerula tadshikorum M. Pimen.On the basis of physicochemical and spectral investigations, the structure of 7-(9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin is proposed for (I) and that of 7-(4-acetoxy-9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin for (II).All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov State University. Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 593–599, September–October, 1976.     

New chiral acyclic analogs of 2′-deoxynucleosides

Convenient methods for the synthesis of chiral 2,3-seco-2-deoxynucleosides were developed. An isopropylidene protective group was used to block the 3,5-hydroxy groups in 2,3-seco-uridine. Conversion of the hydroxymethyl group to a methyl group was accomplished by chlorination with a mixture of CCl₄ and Ph₃P with subsequent reduction with n-Bu₃SnH. 2,3-seco-2-Deoxyuridine was obtained after deacetonation. The (S) enantiomer was similarly synthesized starting from 1-(-D-arabinofuranosyl)uracil. 3-O-tert-Butyldimethylsilyl-5-O-(p-monomethoxytrityl)-2,3-seco-2-deoxyuridine, which has optically active centers at C₍₁₎ and C₍₄₎, was also synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 822–826, June, 1988.The authors thank Professor M. Ya. Karpeiskii for his constant interest in this research.     

Über Tetrahydrospiro [cyclohexan-1,4′(1′H)-chinazolin]-2′(3′H)-one

Zusammenfassung Cyclohexanon bzw. Cyclopentanon sowie ihre durch Aldolreaktion entstehenden Dimeren reagieren mit Harnstoff im sauren Medium zu 5,6,7,8-Tetrahydrospiro[cyclohexan-1,4(1H)-chinazolin]-3(2H)-onen (2) bzw. zum Dihydrospiro-(cyclopentan-1,4(1H)-5H-cyclopenta[d]pyrimidin)-2(3H)-on (10). Substituierte Harnsotoffe geben Gemische der isomeren 5,6,7,8-Tetrahydro- und 4a,5,6,7-Tetrahydroverbindungen (2, 3) bzw. 6,7-Dihydro-tH- und 5,6-Dihydro-4aH-verbindungen (10, 11). Charakteristisch für2 (3),10 (11) ist die Reaktivität der Kernstellen 8 bzw. 7 gegenüber elektrophilen Agentien (2f-v, 3f-j, 9 a-i, 10 d-f). Äthylmalonsäurebis-trichlorphenylester bzw. Formaldehyd und prim. Amine führen2 in ein partiell hydriertes 1H-Pyrido[3,2,1-ij]chinazolintrion (6) bzw. 1H-Pyrimido[5,6,1-ij]chinazolinon (7) über. Die 1-Alkylverbindungen (2) geben mit Formaldehyd und primären Aminen Hexahydro-8a-hydroxy-4a,8-propanospiro-(cyclohexan-1,4(1H)-pyrido[4,3-d]pyrimidin)-2(3H)-one (8).

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Heterocycles, XXV: tetrahydrospiro [cyclohexane-1,4(1H)-quinazoline]-2(3H)-ones

Cyclohexanone and cyclopentanone, resp., as well as their dimers (formed by aldol reaction) react with urea in the presence of acids to 5,6,7,8-tetrahydrospiro[cyclohexane-1,4-(1H)-quinazoline]-3(2H)-ones (2) and to the dihydrospiro-(cyclopentane-1,4(2H)-5H-cyclopenta[d]pyrimidine)-2(3H)-one (10), resp. Substituted ureas give the isomeric 5,6,7,8-tetrahydro- and 4a,5,6,7-tetrahydro compounds (2, 3), and 6,7-dihydro-5H- and 5,6-dihydro-4aH-compounds (10, 11), resp. Characteristic for2 (3),10 (11) is the reactivity of the nuclear places 8 and 7 with electrophilic agents (2f-v, 3f-j, 9a-i, 10d-f). Ethylmalonic acid bistrichlorophenylester resp. formaldehyde and primary amines react with2 to the partially-hydrogenated 1H-pyrido[3,2,1-ij]-quinazolinetrione (6) and 1H-pyrimido[5,6,1-ij]-quinazolinone (7), resp. The 1-alkyl compounds (2) give with formaldehyde and primary amines hexahydro-8a-hydroxy-4a, 8-propanospiro(cyclohexane-1,4-(1H)-pyrido[4,3-d]pyrimidine)-2(3H)-ones (8).

     

Structures of akiferidin and akiferidinin

Summary The roots ofFerula akitschkensis have yielded two new esters — akiferidin and akiferidinin — for which the structures of 6-0-(3,4-dihydroxybenzoyl)ferutinoI and 2-0-angeloyl6-0-(3,4-dihydroxybenzoyl)akichenol, respectively, have been proposed.Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 725–727, November-December, 1978. Original article submitted June 30, 1978.     

Preparation of 8-(5-oxoindeno [3,2-b]-4-pyridyl)-1-naphthoic acids

The condensation of 1-(1,3-indanedion-2-ylidene)-2-acenaphthenone with imines of -dicarbonyl compounds gave 2,5-dioxospiro 1,4,acenaphthene-1,4-dihydroindeno-[3,2-b]pyridines. Oxidation of the pyridines with air oxygen at room temperature without catalysts brings about cleavage of the C-C bond to give 8-(5-oxoindeno[3,2-b]-4-pyridyl)-1-naphthoic acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 210–212, February, 1972.     

Synthesis of the bis(2′-chloroethyl) amide of β-(8-guanyl)propionic acid

The synthesis of -(8-guanyl)propionic acid and its chloride, methyl ester, bis(2-hydroxyethyl)amide, and bis(2-chloroethyl)amide has been effected. The latter readily rearranges under certain conditions into 2-chloroethylaminoethyl -(8-guanyl)propionate.     

The quest for a stable silyne, RSi ≡ CR′. The effect of bulky substituents [1]

The two major fundamental obstacles which so far have prevented theisolation of stable silynes, RSiCR (1), are: (a)the existence of more stable isomers, e.g., RRC=Si: (2) and(b) their extremely facile (exothermic) dimerication. The steric andelectronic effects of various substituents R and R (R = alkoxy,alkyl, aryl and silyl; R = alkyl and aryl groups) on the stability ofRSiCR relative to the isomeric RRC=Si:(E(1-2)), and on the energy of dimerization tothe corresponding 1,3-disilacyclobutadienes (E(D)), werestudied computationally using density functional theory (DFT) and theONIOM method. The goal was to find a combination of substituents thatwill make RSiCR more stable than RRC=Si: and whichwill also prevent its dimerization. For R = R = H,E(1-2)) = 40.7 kcal/mol (i.e., 2 islower in energy than 1), and E(D) = –104.0kcal/mol. 1, R = OH, R = m-Tbt 2,6-bis[bis(silyl)methyl]phenyl, is by 11.1 kcal/mol morestable than the isomeric silylidene 2. However, thedimerization of 1, R = OH, R = m-Tbt remains highlyexothermic (by 101 kcal/mol). 1, R = R = m-Tbt and1, R = (t-Bu)₃Si, R = m-Tbt, are by 5.8 and 2.0kcal/mol, respectively, less stable than the corresponding 2.However, the dimerization of 1, R = (t-Bu)₃Si, = m-Tbt is exothermic by only 12 kcal/mol. For1, R = (t-Bu)₃Si, and R = Tbt 2,6-bis[bis(trimethylsilyl)methyl]phenyl, the corresponding1,3-disilacyclobutadiene dimer 3, dissociates spontaneously.Thus, (t-Bu₃Si)SiCTbt is predicted to be kineticallystable towards both, isomerization to (t-Bu₃Si)TbtC=Si: anddimerization to 3, making it a viable synthetic target. Thereported energies were calculated atB3LYP/6-31G^**//B3LYP/3-21G^*; good agreement is found betweenthe DFT and the ONIOM results.     

Spektrophotometrische und fluorometrische Bestimmung von Myricetin (3,3′,4′,5,5′,7-Hexahydroxy-Flavon)

Zusammenfassung Myricetin (3,3,4,5,5,7-Hexahydroxyflavon) wird aus Pflanzenextrakten chromatographisch abgetrennt, mit Methanol eluiert. Das gelbgrüne Fluoreszenzlicht seines Aluminiumchelats wird in Gegenwart von Essigsäure und Ammoniumacetat gemessen. 10^–4% Myricetin lassen sich mit einem relativen Fehler von ±4% bestimmen.

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Spectrophotometric and fluorometric determination of myricetin (3,3,4,5,5,7 -hexahydroxyflavone)

Summary Myricetin (3,3,4,5,5,7-hexahydroxyflavone) is separated chromatographically from plant extracts and eluted with methanol. The yellow-green fluorescent light of its aluminium chelate is measured in the presence of acetic acid and ammonium acetate. 10^–4% Myricetin can be determined with a relative error of ±4%.

     

Application of the Arbuzov reaction to establish the structure of D-mannitol tricyclic triethyl triphosphite

Conclusions The previously expressed theory that the tricyclic triethyl triphosphite of D-mannitol is 2-ethoxy-4, 5-bis-(2-ethoxy-1, 3, 2-dioxaphospholan-4-yl)-l,3,2-dioxa-4-phospholane was corroborated on the basis of the differential-thermal analysis and³¹P NMR data.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1390–1395, June, 1972.     

New acylated flavone glycoside fromGnaphalium uliginosum

A new acylated flavone glycoside has been isolated for the first time from the herb marsh cudweed, and for it the structure of 6-caffeyl-7--D-glucopyranosyloxy-4,5-dihydroxy-3,6dimethoxyflavone has been established. In addition, the aglycone, identified as 4,5,7-trihydroxy-3,6-dimethoxyflavone has been isolated. The identifications were made on the basis of UV, IR, PMR, and mass spectra, the products of alkaline and acid hydrolyses, and the results of elementary analysis, melting points, and specific rotations.Vitebsk Medical Institute. All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 311–315, May–June, 1979.     

Synthesis of some 5′-O-amino acid derivatives of uridine as potential inhibitors ofUDP-glucuronosyltransferase

Summary In an attempt to develop potential inhibitors ofUDP-glucuronosyltransferase, some 5-O-amino acid derivatives of uridine were synthesized. N-protectedL-amino acids were coupled at the 5-O-position of 2,3-O-isopropylideneuridine by esterification employing the method of symmetrical anhydrides in presence of 4-dimethylaminopyridine, 5-O-(N-benzyloxycarbonyl-O-tert.butyl-L-threonl)-23-O-isopropylideneuridine (1), 5-O-(N-tert.butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylideneuridine and (2), 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (3), and 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (4) were obtained in good yield after column chromatography on silica gel. The treatment of2 withTFA/CH₂Cl₂ (6:1) at room temperature for 30 min led to a selective removal of theBoc group without deblocking of the 2,3-O-isopropylidene group of uridine. Treatment of2 withTFA/H₂O (5:1) at room temperature for 1 h, however, released bothBoc and 2,3-isopropylidene groups. TheZ group of1 was deprotected by catalytic hydrogenolysis over 10% Pd/C/ammonium formate.

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Synthese von 5-O-Aminosäurederivaten des Uridins als potentielle Inhibitoren derUDP-Glukuronosyl-Transferase

Zusammenfassung In einem Versuch, potentielle Inhibitoren derUDP-Glukuronosyl-Transferase zu entwickeln, wurden einige 5-O-Aminosäurederivate des Uridins synthetisiert. N-GeschützteL-Aminosäuren wurden durch Veresterung mit der 5-O-Position des 2,3-isopropylidenuridins gekuppelt (Methode der symmetrischen Anhydride in der Gegenwart von 5-Dimethylaminopyridin). Solcherweise wurden 5-O-(N-Benzyloxycarbonyl-O-tert.butyl-L-threonly)-2,3-O-isopropylidenuridin (1), 5-O-(N-tert.Butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylidenuridin (2), 5-O-(N-tert.Butyloxycarbonyl-L-leucyl)-2,3-O-isopropylidenuridin (3) und 5-O-(N-tert.Butyloxycarbonyl-L-valyl)-2,3-O-isopropylidenuridine (4) nach Säulenchromatographie (Kieselgel) in guter Ausbeute hergestellt. Die Behandlung von2 mitTFA/CH₂Cl₂ (6:1) bei Zimmertemperatur (30 min) führte zu einer selektiven Abspaltung derBoc-Gruppe ohne Deblockierung der 2,3-O-Isopropylidengruppe des Uridins. Eine Behandlung von2 mitTFA/H₂O (5:1) bei Zimmertemperatur für 1 Stunde führte hingegen zur Abspaltung sowohl derBoc als auch der 2,3-O-Isopropylidengruppe. DieZ-Gruppe von1 wurde durch katalytische Hydrogenolyse auf 10% Pd/C/Ammoniumformiat abgespalten.

     

Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.     

Diacetylenic Derivatives of Fe2(CO)6(μ-EE′): Spectroscopic Investigations of Fe2(CO)6{μ-EC(H) = C(C≡ CMe)E′} (E = E′, E ≠ E′; E, E′ = S, Se, Te)

The diacetylenic adducts, Fe₂(CO)₆{-EC(H) = C(C CMe)E} (E = E, E E; E, E = S, Se, Te) (1–8) have been obtained from the room temperature stirring of Fe₂(CO)₆(-EE) with HC CC CMe in methanol solvent containing sodium acetate. Compounds 1–8 have been characterized by IR and multinuclear NMR (¹H, ¹³C, ⁷⁷Se, and ^l25Te) spectroscopy. Trends in the chemical shifts of ⁷⁷Se and ¹²⁵Te NMR spectra of Fe₂(CO)₆{-EC(H) = C(C CMe)E} with a variation of EE are discussed.     

Coumarins of theLibanotis buchtormensis

Conclusions From the roots ofLibanotis buchtormensis (Fisch.) D.C. have been isolated the furocoumarins bergapten, isoimperatorin, a pyranocoumarin, xanthogallol, and a new coumarin buchtormin C₁₉H₂₀O₅, for which the structure (+)-3-(,-dimethylacryloxy)-2,2-dimethyl-3, 4-dihydropyrano-5, 6:8, 7-coumarin has been proposed and confirmed by synthesis.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 3, pp. 145–149, 1968     

1,4-bis(4′-hydroxy-1′,2′,5′-trimethyl-4-piperidyl)-1,3-butadiyne and its derivatives

1.4-Bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)-1.3-butadiyne has been synthesized from the individual isomers of 4-ethynyl-1,2,5-trimethyl-4-piperidol. Hydrogenation, bromination, and cleavage have given, respectively, 1,4-bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)butane, 1,4-bis(4-nydroxy-1,2,5-trimethyl-4-piperidyl)-1,2,3,4-tetrabromo-1, 3-butadiene, and 4-(1,3-butadiynyl)-1,2,5-trimethyl-4-piperidol.     

1,2-Dimethylimidazobenzo-1′, 2′, 3′-thiadiazoles and derived cyanine dyes

New tricylic heterocyclic systems and their methyl derivatives are synthesized. They are 2-methylimidazo[5, 4-e]benzo-1, 2, 3-thiadiazole, 2-methylimidazo[5, 4-g]benzo-1, 2', 3-thiadiazole, 1, 2-dimethylimidazo[5, 4-g]benzo-1, 2, 3-thiadiazole, and 1, 2-dimethylimidazo[5, 4-g]benzo-1, 2, 3-thiadiazole. Quaternary salts of the 1, 2-dimethyl derivatives are used to prepare symmetrical and unsymmetrical trimethinecyanines and dimethinemerocyanines containing rhodanine groups. The absorption maxima of the dyes are displaced towards the long wavelength region compared with imidacarbocyanines. It is shown that when 1, 2-dimetnyl-5-aminobenzoimidazole is thiocyanated, the thiocyano group enters the benzoimidazole ring at position 4, and that 1, 2-dimethylimidazo[5, 4-e] benzo-1, 2, 3-thiadiazole is less basic than its isomer 1, 2-dimethylimidazo[5, 4-g]benzo-1, 2, 3-thiadiazole.     

Vanadyl ion complexes with nucleotides

Summary Complexes of adenosine-5-triphosphate, adenosine-5-monophosphate, guanosine-5-monophosphate, inosine-5-monophosphate, cytidine-5-monophosphate and uridine-5-monophosphate with vanadyl ion, have been studied in the solid state by i.r. spectroscopy and magnetochemically. All complexes have normal magnetic moments, very close to the spin-only values. From the i.r. spectra it is suggested that the vanadyl ion is interacting with adenosine-5-triphosphate, through the N-1 of the purine ring, with adenosine-5-monophosphate, guanosine-5-monophosphate, inosine-5-monophosphate, through the N-7 of the purine ring, with cytidine-5-monophosphate through the N-3 of the pyrimidine ring, and most probably through the phosphate group with uridine-5-monophosphate. The complexes of vanadyl ion with the nucleotides are probably polymeric.