Reactions of regioisomeric 3,3-dimethyl- and 2,2-dimethyl-6-trifluoromethyl-2,3-dihydro-4-pyrones with N-nucleophiles

Reactions of 2,2-dimethyl-6-trifluoromethyl-2,3-dihydro-4-pyrone with ethylenediamine, hydrazine, or hydroxylamine yield 5-methyl-7-trifluoromethyl-2,3-dihydro-1H-1,4-diazepine, 3(5)-(2-hydroxy-2-methylpropyl)-5(3)-trifluoromethylpyrazole, and 5-hydroxy-3-(2-hydroxy-2-methylpropyl)-5-triflouromethyl-Δ², respectively. The same compounds were obtained from 2-amino-1,1,1-trifluoro-6-hydroxy-6-methylhept-2(Z)-en-4-one and 2-hydroxy-6, 6-dimethyl-2-trifluoromethyltetrahydro-4-pyrone.     

Derivatives of azaindoles. 65. Synthesis of 1-benzyl-4-methyl-5-cyano-6-hydroxy-7-azaindoline

Treatment of the ammonium (I) or benzylammonium salt of 2,6-dihydroxy-3-(-hydroxyethyl)-4-methyl-5-cyanopyridine (II) with a mixture of benzylamine and phosphorus pentoxide yielded 2-benzylamino-3-(-hydroxyethyl)-4-methyl-5-cyano-6-hydroxypyri-dine (III), which, when heated with phosphorus oxychloride, is converted to 1-benzyl-4-methyl-5-cyano-6-hydroxy-7-azaindoline (IV). The products of thermal fragmentation of II with benzylamine were studied by the method of chromato-mass spectrometry. In addition to compound III, N,N-dibenzylurea (V) and the dibenzylamide of malonic acid (VI) were preparatively isolated from the reaction products. The cyclization of I and II to 4-methyl-6-hydroxy-2,3-dihydro-7-azabenzofuran (VII) and 4-methyl-5-cyano-6-hydroxy-2,3-dihydro-7-azabenzofuran (VIII) was carried out. Heating VIII with benzylamine at 200–210°C led to compound III.For communication 64, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1105–1109, August, 1984.     

Transformations of 2-(3-Hydroxy-3-methyl-1-butynyl)adamantan-2-ol >Catalyzed by Acids

Reaction of 2-(3-hydroxy-3-methyl-1-butynyl)adamantan-2-ol with acetonitrile under Ritter reaction conditions is accompanied by isomerization and partial hydration where the water addition to the triple bond occurs nonselectively. As a result of reaction carried out in the presence of 8 equiv of sulfuric acid a mixture was obtained of N ²-[4-(1-acetylamino-2-adamantyl)-2-methyl-3-butyn-2-yl]acetamide, N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-2-oxo-3-butyl]-acetamide, and N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-1-oxo-3-butyl]acetamide in ~10:3:2 ratio. In the presence of 2 equiv of the acid the mixture obtained consisted of N ²-[4-(1-acetylamino-2-adamantyl)-2-methyl-3-butyn-2-yl]acetamide, N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-2-oxo-3-butyl]acetamide, and 1-(1-acetylamino-2-adamantyl)-3-methyl-2-buten-1-one in the same ratio. In Rupe reaction conditions we obtained instead of the expected ,-unsaturated ketones a mixture of 1-(1-hydroxy-2-adamantyl)-3-hydroxy-3-methylbutan-1-one and 1-(1-hydroxy-2-adamantyl)-3-hydroxy-3-methylbutan-2-one in a 5:3 ratio.     

Identification and synthesis of volatiles released by the myxobacterium Chondromyces crocatus

Cultures of the myxobacterium Chondromyces crocatus on agar plates were analysed by closed-loop-stripping analysis or solid phase micro extraction. The odour profiles consist mainly of pyrazines, sesquiterpenoids and some aromatic compounds, summing up to more than 50 components. Several new pyrazines as 2-(1-hydroxy-1-methylethyl)-3-methoxypyrazine (9), 2-(1-hydroxy-1-methylpropyl)-3-methoxypyrazine (10), and 2-(1-hydroxy-2-methylpropyl)-3-methoxypyrazine (11) were identified besides several known pyrazines. A major pyrazine occurring in most samples was 2,5-bis-(1-methylethyl)pyrazine (3). While the well known sesquiterpenoid geosmin (1) was present in low amounts, the related compound (1(10)E,5E)-germacradien-11-ol (21) was identified in most samples in larger quantities. Other prominent sesquiterpenoids not reported before from microorganisms were (6S,10S)-6,10-dimethylbicyclo[4.4.0]dec-1-en-3-one (16), which was accompanied by smaller amounts of several derivatives. The biosynthesis of these compounds is discussed in relation to the recently proposed biosynthetic pathways to 1 and 21.     

Oxiranyl β-aminovinyl ketones. 5. Transformation of 2-methyl-2-(1-halogenoalkyl)-3(2h)-furanones into oxiranyl β-aminovinyl ketones

In reaction with amines 2-methyl-2-(1-halogenoalkyl)-3(2H) furanones form S-amino-1-halogeno-3-hydroxy-2-methyl-4 penten-3-ones and 6-amino-2-halogeno-3-hydroxy-3-methyl-5-hexen-3-ones, which are converted by the action of bases into the corresponding oxiranyl -aminovinyl ketones.Belorussian State University, Department of Organic Chemistry and Chemistry of High-Molecular Compounds, Minsk. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 609-612, May, 1995. Original article submitted April 11, 1995.     

Acyclic analogs of nucleosides. Synthesis and in vitro antiviral activity of hydroxyalkyl-2-(trifluoromethylthiomethyl) benzimidazoles

In a search for novel antiviral compounds of the doubly modified nucleoside type, we have prepared 1-(4-hydroxy-2-oxabutyl)-, 1-(4-hydroxy-3-hydroxymethyl-2-oxabutyl)-, 1-(4-hydroxy-1-hydroxymethy1-2-oxabutyl)-, 1-(4-hydroxy-1-methyl-2-oxabutyl), 1-(4,5-dihydroxy-2-oxapentyl)-, 1-(5-hydroxy-2-oxapentyl), 1-(5-hydroxy-1-chloromethyl-2-oxapentyl)-, and 1-(6-hydroxy-1-chloromethyl-2-oxahexyl)-2-(trifluoromethylthiomethyl)benzimidazole. They were obtained by condensing the trimethylsilyl derivative of 2-(trifluoromethylthiomethyl) benzimidazole with alkylating agents in the presence of an equimolar mixture of trifluoromethanesulfonic acid and trimethylchlorosilane. These nucleoside analogs showed moderate antiviral activity against some RNA viruses.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 493–496, April, 1989.     

Synthesis of α,ω-Bis(3-methyl- or 3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydro-1-pyrimidinyl)alkanes

The reactions of stoichiometric amounts of sodium salts of 2-hydroxy-3-methyl-4-oxo-3,4-dihydropyrimidine or 2-hydroxy-3,6-dimethyl-4-oxo-3,4-dihydropyrimidine and dibromoalkanes in dimethylformamide were used to synthesize ,-bis(3-methyl- or 3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydro-1-pyirimidinyl)alkanes with 1 and 3-5 methylene units in the hydrocarbon brigde.     

Synthesis and products of hydrolysis of 2-methyl-5-(β-arylacrylyl)-2-oxazolines

The condensation of 2-methyl-5-acetyl-2-oxazolines with p-R-substituted benzaldehydes in the presence of bases gave the corresponding 2-methyl-5-(-aryl-acrylyl)-2-oxazolines, the hydrolysis of which with hydrochloric acid leads to hydrochlorides of alkyl-substituted 1-(p-R-styryl)-2-acetoxy-3-aminobutan-1-ones. Treatment of the latter with bases gives 1-(p-R-styryl)-2-hydroxy-3-N-acetyl-2, 3-alkylbutan-1-ones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1025–1027, August, 1982.     

2-Polyfluoroalkylchromones. 11. Synthesis and structures of 5-hydroxy-3-(2-hydroxyaryl)-5-polyfluoroalkyl-Δ2-pyrazolines and 3(5)-(2-hydroxyaryl)-5(3)-polyfluoroalkylpyrazoles

The reaction of 2-hydroxy-2-polyfluoroalkylchroman-4-ones with hydrazine affords 5-hydroxy-3-(2-hydroxyaryl)-5-polyfluoroalkyl-²-pyrazolines, whereas 2-polyfluoroalkylchromones under similar conditions produce 3(5)-(2-hydroxyaryl)-5(3)-polyfluoroalkylpyrazoles. 5-(2-Hydroxyaryl)-1-methyl-3-polyfluoroalkylpyrazoles were synthesized in the reaction with methylhydrazine, and the reaction with phenylhydrazine afforded regioisomeric 3(5)-(2-hydroxyphenyl)-1-phenyl-5(3)-polyfluoroalkylpyrazoles.     

Novel One-Pot Multicomponent Synthesis of Substituted 2,3-Dihydro-2-(6-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazin-3-yl)phthalazine-1,4-diones and Substituted 3-[3-(N′-Benzylidene-hydrazino)-7H-[1,2,4] triazolo[3,4-b][1,3,4]thiadiazin-6-yl]-4-hydroxy-6-methyl-pyran-2-ones

A one-pot procedure has been developed for the synthesis of substituted 2,3-dihydro-2-(6-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-7H-[1,2,4]triazolo[3,4-b] [1,3,4]thiadiazin-3-yl)phthalazine-1,4-diones by reaction of 3-(2-bromoacetyl)-4-hydroxy-6-methyl-2H-pyran-2-one, 4-amino-5-hydrazino-4H-[1,2,4]triazole-3-thiol, and phthalic anhydrides in acetic acid medium. Similarly, a one-pot, three-component synthetic procedure has been developed for substituted 3-[3-(N¹-benzylidene-hydrazino)-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazin-6-yl]-4-hydroxy-6-methyl-pyran-2-ones from 3-(2-bromoacetyl)-4-hydroxy-6-methyl-2H-pyran-2-one, 4-amino-5-hydrazino-4H-[1,2,4]triazole-3-thiol, and various aromatic aldehydes in absolute ethanol and a few drops of glacial acetic acid.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

1,4-Carbazolchinone ausp-Benzochinon und primären aliphatischen Aminen. Das vermeintliche und das wahre 2-Methylamino-benzochinon

The compound which is obtained in the reaction of 1,4-benzoquinone with methylamine in chloroform was supposed to be 2-methylaminobenzoquinone; actually it is 6-hydroxy-9-methyl-3-methylamino-1,4-carbazolquinone. The structure is proved by spectroscopic methods, through derivates, zinc dust distillation and via synthesis from 2,5,2,5-biphenyl-diquinone. A second main product, 2,5-bis(methylamino)quinone, is obtained; varying the reaction conditions shows especially the influence of the solvent. One of the intermediate products is the true 2-methylamino-1,4-quinone. Other substituted 9-alkyl-3-alkylamino-6-hydroxy-1,4-carbazolquinones can be prepared by reaction with the corresponding primary amines.

     

Some reactions of tetrafluoroethylene oligomers

As part of a programme to prepare and evaluate a series of perfluoro- chemicals for use as inert fluids, the fluorinations of some tetrafluoroethylene oligomers over cobalt (III) fluoride have been studied.Fluorination of perfluoro-3,4-dimethylhex-3-ene (tetramer) and perfluoro-4-ethyl-3,4-dimethylhex-2-ene (pentamer) over CoF₃ at 230°C and l45°C respectively afforded the corresponding saturated fluorocarbons however, at 250°C, pentamer gave predominantly the saturated tetramer. The thermal behaviour of these saturated fluorocarbons alone and in the presence of bromine and toluene has been studied.Pyrolysis of pentamer over glass beads at 500°C gave perfluoro-1,2,3- trimethylcyclobutene and isomers of perfluoro-2,3-dimethylpenta-1,3- diene. Under similar conditions perfluoro-2-(1-ethyl-1-methylpropyl). 3-methylpent-1-ene (hexamer) gave perfluoro-1-methyl-2-(1-methyl- propyl)-cyclobut-1-ene and perfluoro-2-methyl-3-(1-methylpropyl)-buta- 1,3-diene.These reactions and the structural elucidation of the products will be discussed.     

Synthesis of 2-oxohexahydrothieno[3,4-d]imidazole derivatives

Conclusions We synthesized the cis-3- and 4-methyl-2-oxo-6-(-carboxybutyl) hexahydro [3,4-d]-imidazoles by the reduction of the 3- and 4-methyl-2-oxo-2,3-dihydro-6-(carboxybutyl)-1H-thieno [3,4-d] imidazoles with HSiEt₃ in CF₃COOH and subsequent alkaline hydrolysis of the intermediate methyl ethers.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1634–1636, July, 1980.The authors express their gratitude to Prof. A. Mark (France) for supplying the sample of 2-oxo-4-methyl-6-(6-carboxybutyl)hexahydrothieno[3,4-d]imidazole.     

Synthesis and molecular structure of 2,4,8a-triaryl-6-methylperhydro[1,3,2]dioxaborinino[5,4-c]pyridines

Condensation of arylboronic acids with 4-hydroxy-3-(-hydroxybenzyl)-1-methyl-4-phenylpiperidine afforded 2,4,8a-triarylperhydro[1,3,2]dioxaborinino[5,4-c]pyridines. The molecular structure of 6-methyl-2,4,8a-triphenylperhydro[1,3,2]dioxaborinino[5,4-c]pyridine was established by X-ray diffraction analysis.     

Synthese des 6- und 7-Methyl-spiro[4.5]deca-6,9-dien-8-ons

Zusammenfassung Es werden die Synthesen folgender Verbindungen beschrieben: -(4-Hydroxy-3-methylphenyl)buttersäure, 4-(4-Hydroxy-3-methylphenyl)-1-butanol, 7-Methyl-spiro[4.5]deca-6,9-dien-8-on, -(4-Hydroxy-2-methylphenyl)buttersäure und dessen Methylester, 4-(4-Hydroxy-2-methylphenyl)-1-butanol und 6-Methyl-spiro[4.5]deca-6.9-dien-8-on.

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The synthesis of the following compounds is described: -(4-hydroxy-3-methylphenyl)-butyric acid, 4-(4-hydroxy-3-methylphenyl)-butanol-(1), 7-methyl-spiro[4.5]deca-6.9-dien-8-one, -(4-hydroxy-2-methylphenyl)-butyric acid and its methyl ester, 4-(4-hydroxy-2-methylphenyl)-butanol-(1) and 6-methyl-spiro[4.5]deca-6.9-dien-8-one.

     

Alkaloids ofHaplophyllum foliosum. III. Structure of folidine

The new alkaloid folidine with mp 148–149°C (acetone-petroleum ether) has been isolated from the epigeal part of the plantHaplophyllum foliosum Vved., and on the basis of spectral characteristics and passage to the known alkaloid folifidine (8-hydroxy-4-methoxy-1-methyl-2-quinoline) its structure has been established as 4-methoxy-1-methyl-8-(2-oxo-3-methylbutoxy)-2-quinolone.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 823–824, November–December, 1985.     

Structure of some components of the roots of Prangos ferulacea

Summary From a methanolic extract of the roots ofPrangos ferulacea (L) Lindl., growing in the Nakhichevan ASSR, in addition to the compounds found previously, another six substances (I–VI) have been isolated, of which (I) and (VI) have been identified as, respectively, meransin hydrate monoacetate, found for the first time in nature, and umbelliferone: and in the study of a crystalline mixture obtained from the resin of the roots of the plant under investigation collected in Armenia, two coumarins — (VII) and (VIII) — have been isolated.On the basis of a study of IR, NMR, and mass spectra and chemical properties, the structures of the six new cumarin derivatives (II–V, VII, and VIII) have been established. Compound (II) has the structure of 8-(3-methylbutenyloxy)furo-2,3:7,6-coumarin and has been called feruliden; (III) is 7-hydroxy-8-(3-hydroxy-2-senecioyloxyisopentyl) coumarin and has been called ferudiol; (IV) is 7-hydroxy-8-(3-methoxy-2-senecioyloxyisopentyl) coumarin; (V) is 5-[1-(2,3-dihydroxy-3-methylbutyroyloxy)-1-methylethyl]-4,5-dihydrofuro-2,3:7,6-coumarin and has been called lindiol; (VII) is 8-(2-hydroxy-3-methylbut-3-enyloxy)-7-methoxycoumarin and has been called ferudenol; (VIII) is 7-methoxy-8-(3-methyl-2-oxobut-3-enyl)coumarin and has been called prangone.Leningrad Sanitary-Hygenic Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 568–574, September–October, 1974.     

Enthalpies of proton transfer of hydroxy amines and maltol in methanol-water mixtures by direct calorimetry

Enthalpies of proton transfer in methanol-water mixtures (0–90 wt. % methanol) have been measured by direct calorimetry for the bases 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and 2,2-bis(hydroxymethyl)-2,2,2-nitrilotriethanol at 25°C. Also reported are the data for 3-hydroxy-2-methyl-4-pyrone. The results are discussed in terms of an adaptation of classical electrostatic formula.     

Reaction ofβ,β -dimethyldivinyl ketone with 2,5-dimethyl- and 1,2,5-trimethyl-4-piperidones

1-(3-Oxo-5-methyl-4-hexen-1-yl)-2,5-dimethyl-4-piperidone, 5-(3-oxo-5-methyl-4-hexen-1-yl)-2, 5-dimethyl-4-piperidone, and 5-(3-oxo-5-methyl-4-hexen-1-yl)-1,2,5-trimethyl-4-piperidone were synthesized. In the absence of a catalyst,-dimethyldivinyl ketone adds to 2,5-dimethyl-4-piperidone at the 1-position, while in the presence of alkali it adds at the 5-position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 350–351, March, 1971.     

Vinyl Ethers Containing an Epoxy Group: XXI. Synthesis and Acid-Catalyzed Cyclization of 1-[ω-(Vinyloxy)alkoxy]-3-(2-propynyloxy)-2-propanols- A Simple Route to 2-Propynyloxymethyl-Substituted Cyclic Polyethers

Base-catalyzed reaction of 2-[-(vinyloxy)alkoxy]methyloxiranes with 2-propynyl alcohol (3 wt % of t-BuOK, 60-85°C, 3-12 h) afforded first reperesentatives of the 1-[-(vinyloxy)alkoxy]-3-(2-propynyloxy)-2-propanol series in up to 99% yield. Treatment of 1-[2-(vinyloxy)ethoxy]- and 1-[2-(vinyloxy)ethoxyethoxy]-3-(2-propynyloxy)-2-propanols with trifluoroacetic acid (0.5 wt. %) in dry diethyl ether resulted in cyclization with formation of up to 96% of (2-methyl-1,3,6-trioxocan-4-yl)methyl- and (2-methyl-1,3,6,9-tetraoxacycloundecan-4-yl)methyl 2-propynyl ethers.