Derivatives of n-(pyrimid-4-yl)ethylamine

In order to find compounds possessing antibacterial activity, a number of new derivatives of N-(pyrimid-4-yl)ethylamine have been synthesized from 5-amino-4, 6-dichloropyrimidine, 2-amino-4, 6-dichloro-pyrimidine, 4, 6-dichloro-2-phenylpyrimidine, and 2,4-dichloro-6-methylpyrimidine and various ethylamines substituted in the -position. Several derivatives of 4-(4-methylpiperazinyl)pyrimidine have also been obtained. Results of a biological study of the compounds obtained are presented.For part II, see ¦1¦.     

N-(4-Pyrimidyl)ethylamine derivatives

In order to find antitumoral agents, a number of new N-(4-pyrimidyl) ethylamine derivatives have been synthesized from 4,6-dichloropyrimidine, 6-amino-4-chloropyrimidine, 4-chloro-6-hydroxypyrimidine, and various ethylamines substituted in the position.     

Reaktionen des 4,6-Dichlor-5-formylpyrimidins

Zusammenfassung Bei der Methanolyse des 4,6-Dichlor-5-formylpyrimidins (I) tritt neben dem 4,6-Dimethoxy-5-formylpyrimidin (III) auch das 4-Methoxy-6-hydroxy-5-formylpyrimidin (IV) als Reaktionsprodukt [in Verhältnis 11] auf. Das Aldoxim V des 4,6-Dichlor-5-formylpyrimidins ist instabil und geht in das 4-Chlor-5-cyano-6-hydroxypyrimidin (VI) über. Beide Reaktionen werden mit Hilfe möglicher Zwischenprodukte erklärt. Hingegen führt Methanolyse des Dimethylacetals von I in guter Ausbeute zum 4,6-Dimethoxy-5-formylpyrimidin (III). Das 4,6-Dichlordimethylacetal (II) wird durch aufeinanderfolgende Sulfanilamidolyse, Methanolyse und Hydrolyse in das Acetal des 4-Sulfanilamido-6-methoxy-5-formylpyrimidins (IX) verwandelt. Die gleiche Reaktionsfolge wird auch mit dem cyclischen Acetal 5-(2-Dioxolano)-4,6-dichlorpyrimidin zu XII durchgeführt.

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During methanolysis of 4.6-dichloro-5-formylpyrimidine (I) 4-methoxy-6-hydroxy-5-formylpyrimidine (IV) is formed as well as 4,6-dimethoxy-5-formylpyrimidine (III) in a ratio of 11. The aldoxime V of 4,6-dichloro-5-formylpyrimidine is not stable and is converted into 4-chloro-5-cyano-6-hydroxypyrimidine (VI). Both reactions are interpreted by considering possible intermediates. On the other hand, methanolysis of the dimethylacetal of I affords a good yield of 4,6-dimethoxy-5-formylpyrimidine (III). The 4,6-dichlorodimethylacetal (II) is converted into the acetal of 4-sulfanilamido-6-methoxy-5-formylpyrimidine (IX) by sulfanilamidolysis followed by methanolysis and hydrolysis. The same series of reactions has also been applied to the cyclic acetal of 5-(2-dioxolano)-4,6-dichloropyrimidine to give XII.

     

Dissociation and complexation constants of some β-diketone ionophores

The dissociation constants of dibenzoylmethane (DBM), 1-phenyl-3-(p-chlorophenyl)-1,3-propanedion (ETH 245) and 1,13-bis-[4-(3-phenyl-1,3-dioxopropyl)-phenyl]-tridecan (ETH 1224) were potentiometrically evaluated in 80% dioxane medium at 30 °C. The stability constants of DBM complexes with calcium, magnesium and barium as well as those of ETH 245 with magnesium were determined and correlated with the selectivity coefficients of ion-selective electrodes containing DBM as ionophore.     

Synthesis of optically active 9-purinyl-α-amino acids

A general method for the synthesis of optically active 9-purinyl--amino acids by condensation of 5-amino-4,6-dichloropyrimidine with ,-diamino carboxylic acids and subsequent cyclization of the N-(5-amino-4-chloro-6-pyrimidinyl)-amino acids with triethyl orthoformate was developed. A number of 6-substituted -amino--(9-purinyl) carboxylic acids were obtained by nucleophilic substitution of the chlorine atom in the -amino--(6-chloro-9-purinyl) carboxylic acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1690–1695, December, 1982.     

Analogs of purine nucleosides and purine mono-and polynucleotides

A number of 6-substituted 9-(1,5-dihydroxy-3-pentyl)purines were obtained from 5-amino-4,6-dichloropyrimidine. 5-Amino-4,6-dichloropyrimidine reacts with 2-hydroxymethylpyrrolidine to give 4-chloro-5-amino-6-(2-hydroxymethylpyrrolidino)pyrimidine.See [1] for communication IV.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 552–555, April, 1976.     

Synthesis and reduction of esters of N-(4-amino-5-nitro-6-pyrimidyl)amino acids

The reaction of esters of amino acids with 4-amino-6-chloro-5-nitropyrimidine has yielded esters of (4-amino-5-nitro-6-pyrimidyl)amino acids. The reduction of the esters of -(4-amino-5-nitro-6-pyrimidylamino) acids has yielded 4-amino-6-hydroxy-7,8-dihydropteridines. -(4-Amino-5-nitro-6-pyrimidylamino) acids and the ester of N-(4-amino-5-nitro-6-pyrimidyl)--alanine do not cyclize and on reduction give the corresponding diaminopyrimidine derivatives.     

Novel Synthesis of 5-Hydroxy-5α-cholesta-2,7-dien-6-one and Its Criegee Hydroxylation

Cholesterol (1) is used to synthesize again 5-hydroxy-2,7-dien-6-one (5) through the intermediates 2-4. cis-Hydroxylation of 5 with OsO ₄ and subsequent acetylation give steroids 6-8. Dehydration of 5-hydroxy-6-ketone 6 forms the unsaturated compounds 9-11     

Lactam and acid amide acetals. 64. Acylation of enamino ketones of the indolin-3-one and 2-pyrrolin-4-one series and synthesis of 2-indolyl- and 5-pyrrolylacrylic acid derivatives

The reaction of 2-(N,N-dimethylaminomethylene)indolin-3-one and 2-methyl-3-ethoxycarbonyl-5-(N,N-dimethyl aminomethylene)-2-pyrrolin-4-one with acyl halides was used to synthesize immonium salts, the aqueous hydrolysis of which leads to 2-formyl-3-hydroxyindole and 4-hydroxy-5 formylpyrrole derivatives. -Cyano--(2-indolyl)- and -cyano--(5-pyrrolyl)acrylic acid derivatives were synthesized by reaction of immonium salts of the pyrrole series, 4 acyloxy-5-formylpyrrole and 2-formyl-3-acyloxyindole derivatives, with compounds that contain an active methylene group.See [1] for Communication 63.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–348, March, 1991.     

as-Triazin-Derivate,die möglicherweise therapeutische Wirkung besitzen, 15. Mitt.: Synthese von neuen “blockierten 5-substituierten 4-thio-6-azauridinen”

5-Substituted 4-thio-6-azauracils [I, 6-alkylthio-3,4-dihydro-5-thioxo-1,2,4-triazin-3(2H)-ones] have been converted with hexamethyldisilazane in 3-trimethylsilyloxy-5-trimethylsilylthio-derivatives(II). These were condensed with 1-O-acetyl-2,3,5-tri-O-benzoyl-d-ribofuranose in the presence of anhydrous stannic chloride to afford the corresponding 1-(2,3,5-tri-O-benzoyl--d-ribofuranosyl)-4-thioxo-5-substituted-6-azauracil (III).     

Synthesis of chlorine-containing benzisoindolinium salts by base-catalyzed intramolecular cyclization of ammonium salts

It was shown that dialkylpropargyl/3-(p-chlorophenyl)-2,3-dichloroallyl/ammonium salts in an aqueous alkali medium undergo cyclization-dehydrochlorination to give chlorine-containing benzisoindolinium salts. When the ammonium salt contains simultaneously 3-phenyl (or vinyl)propargyl and 3-(p-chlorophenyl)-2,3-dichloroallyl groups, only the latter enters into the cyclization as the diene fragment.Communication 201 of the series Research on amines and ammonium compounds. See [1] for Communication 197.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1481–1483, November, 1988.     

Molecular Recognition Study on a Supramolecular System. Part 21. Inclusion Complexation Thermodynamics of Aliphatic Alcohols by Organoselenium Modified β-Cyclodextrins

The spectrophotometric titrations have beenperformed at 25–40 °C in aqueous solution to give the complexstability constants and the thermodynamic parametersfor the stoichiometric 1 : 1 inclusion complexation ofvarious aliphatic alcohols withmono[6-(phenylseleno)-6-deoxy]--cyclodextrin (2),mono[6-(o-, m-,p-tolylseleno)-6-deoxy]--cyclodextrin (3–5),mono[6-(p-chloro-phenyl-seleno)-6-deoxy]--cyclodextrin(6), mono[6-(benzylseleno)-6-deoxy]--cyclodextrin (7) and mono[6-(naphthaleneseleno)-6-deoxy]--cyclodextrin(8). On thebasis of the present and previous results, themolecular binding abilities and selectivities forguest aliphatic alcohols of the host -cyclodextrinderivatives (2–8) are discussed comparatively and globallyfrom the thermodynamic point of view. Thethermodynamic parameters obtained are criticalfunctions of the size/shape of aliphatic alcohols, andthe position and type of the substituent introduced tothe aromatic ring of -cyclodextrin's sidearm,which are elucidatedin terms of the conformational, electrostatic,hydrogen-bonding, and hydrophobic effects.     

Acylated C-glycosides ofIris lactea

From the epigeal part ofIris lactea two acylated C-glycosylflavones not described in the literature have been isolated. On the basis of chemical transformations, and the results of UV, IR, and NMR spectroscopy, the following structures have been established for them: substance (I) — 5-hydroxy-4',7-dimethoxyflavone 6-C-[0-(2-acetyl--L-rhamnopyranosyl)-(12)-x-acetyl--D-glycopyranoside] (diacetylembinin); substance (II) — 5-hydroxy-4',7-dimethoxyflavone 6-C-[0(2-acetyl--L-rhamnopyranosyl)-(12)-D-glycopyranoside] (acetylembinin). The existence of rotamers for 6-C-glucoflavones has been established for the first time.Leningrad Institute of Pharmaceutical Chemistry, All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 589–595, September–October, 1984.     

Synthesis of Benzofuro-and Benzothieno-Phenanthridones by Twofold Photochemical Dehydrocyclization Reaction

Four new N-(p-chlorophenyl) carboxamides 1–4 of 9-phenanthrene-, 5-naphtho[2, 1-b] furan-, and 5-naphtho-and 4-naphtho[2, 1-b] thiophenecarboxylic acids have been synthesized. All carboxanilides were exposed to UV oxidative irradiation in methanolic solution. In the case of 2 and 3 corresponding benzo[d]-furo[3, 2-f] phenanthridin-10 (9H)-one 5 and benzo [d]-thieno[3, 2-f] phenanthridin-10 (9H)-one 6 are isolated.     

Crystal and molecular structure of 1-aza-6′-(3′-oxo-5′, 5′-dimethyl-δ1′-pyrrolin-3′-yl)methylidene-2,2,7,7-tetramethyl-4-hydroxybicyclo-[2.2.21azaoctane

An x-ray structural study has shown that 6-(3-oxo-5,5-dimethyl-¹-pyrrolin-3-yl)methylidene-2,2,7, 7-tetramethyl-4-hydroxybicyclo[2.2.2]azaoctane is formed as a low-molecular-weight byproduct of the solid-phase polymerization of 1,4-bis(2,2,6,6-tetramethyl-4-hydroxy-4-piperidyl)butadiyne.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 585–587, March, 1990.     

The structure of perforine and haplophyllidine

Conclusions 1. The alkaloids perforine and haplophyllidine isolated from the seeds ofH. perforatum have the developed formulas C₁₆H₁₇N(OH)₂(OCH₃)₂(-O-) and C₁₆H₁₆N(OH) (OCH₃)₂(-O-).2. Perforine is 7-hydroxy-8-(3-hydroxy-3-methylbutyl)-4, 8-dimethoxy-5, 6, 7, 8-tetrahydrofuroquinoline, and haplophyllidine is 7-hydroxy-4, 8-dimethoxy-(3-methyl-2-butenyl)-5, 6, 7, 8-tetrahydrofuroquinoline.3. The transition from perforine to haplophyllidine has been effected by the splitting off of hydrogen chloride from chloroacetylperforine.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 6, pp. 360–367, 1968     

N-methyI-N-(triethoxysilylmethyl) andN-methyl-N-(silatran-1-ylmethyl) substituted glycine and alanine

Organosilicon derivatives of glycine, - and -alanine, and -methylalanine were prepared by the reaction of methyl esters of - and -halocarboxylic acids withN-methylaminomethyltriethoxysilane in the presence of triethylamine. The compounds synthesized were converted into the correspondingN-silatran-l-ylmethyl derivatives. Trimethylsilyliodoacetate reacts withN-methylaminomethyltrietoxysilane to give 2,2-diethoxy4-methyl-1-oxa-4-aza-2-silacyclohexane-6-one. Its reaction with triethanolamine leads toN-methyl-N-(silatran-l-ylmethyl)glycine.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 341–343, February, 1995.     

Prins-Reaktionen mit Arylaldehyden, 5. Mitt.: Zur Umsetzung mit 2-Buten und mit Cyclohexen

By reaction of 2-[(1RS, 2RS)-2-hydroxy-1-methyl-propyl]-2-phenyl-1,3-dithiane (1 a) withcis-2-butene oxide, subsequent reduction and acetalizationc-4,t-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 a) andt-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 b) were synthesized as model compounds. For the same purpose by aldol reaction of cyclohexanone and reduction (1RS, 2SR)-2[(RS)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (7 a), (1RS, 2RS)-2[(SR)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (8 a), and (1RS, 2RS)-2[(RS)-hydroxy-(4-nitrophenyl)methyl]cyclohexanol (8 b) and by acetalization (2 , 4 , 4 a, 8 a)-2,4-bis(4-methoxyphenyl)hexahydro-4H-1,3-benzodioxin (9 a) and (2 , 4 , 4 a, 8 a)-2,4-bis(4-nitrophenyl)hexahydro-4H-1,3-benzodioxin (10 b) were obtained. FromPrins reactions, starting with 2-butene3 a,c-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 c),r-4,t-5-dimethyl-c-6-phenyl-1,3,2-dioxathiane-2,2-dioxide (4), and (2Z, 4E)-1,5-diphenyl-4-methyl-2,4-pentadien-1-on (5), and starting with cyclohexene (E)-3-(4-methoxybenzylidene)cyclohexenyl-4-methoxyphenyl ketone (11) have been isolated in low yields.

4. Mitt.:Griengl, H., Nowak, P., Mh. Chem.109, 11 (1978).     

Structure of ursinoic acid and ursinin

Conclusions On the basis of UV, IR, and NMR spectroscopy, and the preparation of derivatives, the most probable structures of ursinoic acid and ursinin, aromatic oxo acids isolated previously from the roots ofAngelica ursina Rupr. et Schmalh., have been established. It has been shown that the former has the structure 2,2-dimethylpyrano-5, 6:5, 6-(2, 4-dimethoxy)benzoylacetic acid while the second is 2,2-dimethylpyrano-5,6:5, 6-(2-methoxy)benzoylacetic acid.Khimiya Prirodnykh Soedinenii, Vol. 6, No. 4, pp. 421–424, 1970     

Solvent effects on substitution reactions at complexes of the [Fe(CN)5L]3- type in binary aqueous mixtures

Summary The kinetics of replacement of 4,4-bipyridine, (4,4-bipy), and 4-cyanopyridine, (4-CNpy), by cyanide in [Fe(CN)₅-(4,4-bipy)]^3-. at 298 K have been studied in binary aqueous mixtures containing different amounts of t-butanol, methanol, glycerol, ethyleneglycol and sucrose. The plots of logarithms of the limiting rate constantsversus the mole fraction of water are linear over the entire composition range studied, showing the importance of solvation phenomena. A different straight line of log (k_L/s^–1)versus X_H2O is obtained for each mixture, indicating the influence of other solvent parameters on the reaction rate. A multiparameter regression of G _exp with A (acidity vector), B (basicity vector) and G^E is used for both reactions; plots of G _calc versus G _exp are linear with slopes of near unity.