Synthesis of 1′-substituted 4′,4′-dimethyl-6′-methoxy-4′H-spiro[cyclohexane-1,3′-isoquinolines]

The reaction of 1-(4-methoxyphenyl)-1-(1-methylcyclohexyl)ethanol with nitriles in concentrated sulfuric acid afforded 1′-substituted 6′-methoxy-4′,4′-dimethyl-4′H-spiro[cyclohexane-1,3′-isoquinolines] as a result of consecutive Wagner-Meerwein rearrangement and Ritter reaction.     

Synthesis of 4′H-spiro[adamantane-2,3′-isoquinoline] derivatives

Russian Journal of Organic Chemistry -     

Synthesis of 4′-alkyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-morpholin]-5′-ones

N-Boc-protected 8-azaspiro[bicyclo[3.2.1]octane-3,2′-oxirane] reacted with primary aliphatic amines through opening of the epoxide ring with formation of the corresponding amino alcohols which were converted into N-chloroacetyl derivatives. The latter underwent cyclization to N-Boc-protected 4′-alkyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-morpholin]-5′-ones by the action of sodium hydride in DMF, and subsequent treatment with hydrogen chloride in ethyl acetate afforded 8-azaspiro[bicyclo[3.2.1]octane-3,2′-morpholin]-5′-one hydrochlorides.     

Stereoselective [4+2] cycloadditions of tetrazines to 3-oxo- and 3-arylimino-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furans]

Stereoselective inverse-demand [4+2] cycloadditions of 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine and dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate to 4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furans] and 4′-methylene-1′-(4-nitrophenyl)spiro[bicyclo[2.2.1]heptane-3,2′-pyrrolidine] were studied. Cycloadditions took place stereoselectively at the exocyclic CC double bonds to give novel 11:14-isopropylidene-14-methyl-2,3-diaza-8-oxadispiro[5.1.5.2]pentadecane and 11:14-isopropylidene-11-methyl-2,3,8-triazadispiro[5.1.5.2]pentadecane derivatives in 50–98% de. The structures of the novel dispiro compounds were determined by NMR techniques, NOESY spectroscopy and X-ray diffraction.     

Alkylation of pyrimido[5′,4′:5,6]pyrido[3,2-b]indol-4-one derivatives

Alkylation of 11-benzyl-3,11-dihydro-4H-pyrimido[5′,4′:5,6]pyrido[3,2-b]indol-4-one with methyl iodide and methyl bromoacetate in DMF gave 3-alkylpyrimidopyridoindolones as the corresponding salts. The reaction in acetone in the presence of K₂CO₃ yielded 3,6-disubstitution products. Alkylation with DMF dimethyl acetal gave a mixture of the 3- and 6-alkylpyrimidopyridoindol-4-one bases. The structure of 4-oxo-4,6-dihydro-3H-pyrimido-[5′,4′:5,6]pyrido[3,2-b]indol-11-ium chloride (3b) was proved by X-ray diffraction analysis.     

Crystal structure of 1,2‐[4‐butoxybenzoyloxy‐4′‐pentyl]diphenylethane

The crystal structure of 1,2‐[4‐butoxybenzoyloxy‐4′‐pentyl]diphenylethane (C₃₀H₃₆O₃) has been determined by direct methods using single crystal X‐ray diffraction data. It crystallizes in the monoclinic system with space group P2₁/a and Z?=?4. The unit cell parameters are: a?=?8.098(1), b?=?10.926(1), c?=?29.643(2)?Å and β?=?94.01(1)°. The final reliability factor is R?=?0.073 and the goodness of fit is equal to 1.027. The molecular arrangement is very typical, with molecules associated in dimers very closely parallel to the Oz axis. In a given dimer, the backbones of the two molecules run alongside each other; this association can be attributed to strong dipole–dipole interactions through the polar ester and ether groups. In addition these dimers are connected to neighbours via dipole–dipole interactions along the Oy direction. There are numerous very weak van der Waals interactions, particularly between the terminal aliphatic chains.     

Synthesis and Crystal Structure of Spiro[1-bromo-4-methoxy-5-oxa-6-oxo-bicyclo[3.1.0]hexane-2,2′-（3′- cyclohexanoxy-4′-methoxybutyrolactone]

1INTRODUCTIONThecyclopropane-containingnaturalproductshavereceivedconsiderableattentionassynthetictar-getsastheincorporationofrigidifiedcyclopropylmotifintobioactiveanaloguescanleadtoconfor-mablyconstrainedmolecules[1,.Suchmodifica-2]tionsareexpectedtohavesignificanteffectsonbio-activitieswithconcomitantmedicalimplications.Des-pitethegreatadvancesinthisfield,theefficientsyn-thesisofspiro-cyclopropanecompoundsstillremainsaconsiderablechallenge.Particularnoticeisthede-ficiencyinthepreviousm…     

Unexpected high ordering of a [60]Fullerene nitroxide in the nematic phase of 4-4′-azoxyanisole

A nitroxide [60]fullerene adduct containing a pyrrolidine-1-oxyl group has been synthesized. Its orientational order in the nematic phase of the liquid crystal solvent 4,4′-azoxyanisole (PAA) has been measured from the variation of the EPR spectral parameters on passing from the isotropic to the nematic phase. Highly resolved EPR lines allow for precise evaluation of the shifts of the g, a _N and a _H values. Since the g and the hyperfine tensors are known, the order matrix could be obtained. This is compared with the one calculated with a theoretical model based on short range solute-solvent interactions, which predicts a considerable degree of orientation of the molecular axes, despite the almost spherical shape of the molecule. The agreement with experimental findings is quite good and it is further improved if a bent structure of the pyrrolidine ring is taken into account.     

Calorimetric study of 2′-methylacetophenone and 4′-methylacetophenone

Values of the condensed phase standard (p = 0.1 MPa) molar enthalpy of formation for 2′- and 4′-methylacetophenones were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The values of the standard molar enthalpy of vaporization, at T = 298.15 K, were measured by Calvet microcalorimetry. Combining these two values, the following enthalpies of formation in the gas phase, at T = 298.15 K, were then derived: 2′-methylacetophenone, –(115.7 ± 2.4) kJ · mol⁻¹, and 4′-methylacetophenone, –(122.6 ± 2.4) kJ · mol⁻¹. Substituent effects are discussed in terms of stability and compared with other similar compounds. The value of the standard molar enthalpy of formation for 3′-methylacetophenone was estimated from isomerization schemes.     

Investigations of 2,3′-biquinolines 23. Synthesis of 1′-R-1′,4′-dihydro-2,3′-biquinolin-4′-ones by Claisen condensation

A method has been developed for the synthesis of 1′-R-1′,4′-dihydro-2,3′-biquinolin-4′-ones based on the interaction of quinaldine with N-alkyl-N-formylanthranilic acid methyl esters under the conditions of the Claisen condensation. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 409–410, March 2008.     

First Total Syntheses of 4′-0-Geranylisoliquiritigenin And 4′-O-Geranylnarigenin

The title compounds, 4'-0-geranylisoliquiritigenin and 4'-0-geranylnaringenin isolated from Millettia ferruginea and Borania coerulescens respectively, were first synthesized starting from geranyl bromide, 4-hydroxybenzaldehyde and O-hydroxy acetophenones by the condensation reaction and demethoxymethylation as key steps.     

Synthesis and Crystal Structure of 3′-Ethyl 5′-Methyl 1-Benzyl-4′-methyl-2-oxo-3′,4′-dihydrospiro-[indoline-3,2′-pyrrole]-3′,5′-dicarboxylate

The crystal structure of the title compound(C24H24N2O5, Mr = 420.45) has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a = 8.991(1), b = 11.166(1), c = 11.169(1) , α = 91.413(2), β = 105.887(2), γ = 90.992(2)°, V = 1077.8(2) 3, Z = 2, Dc = 1.296 g/cm3, F(000) = 444, μ(MoKα) = 0.091 mm-1, the final R = 0.0466 and wR = 0.1507 for 4185 observed reflections(I 2σ(I)). The single-crystal X-ray diffraction data indicated intermolecular C(17)–H(17)O(4), C(5)–H(5)… O(4) hydrogen bonds and C–H…π interaction in the structure.     

Acylation of 2′,5′,5′-trimethyl-4′,5′-dihydro-4H-spiro-[naphthalene-1,3′-pyrrol]-4-one with 5-arylfuran-2,3-diones

Russian Journal of Organic Chemistry -     

Reaction of tert-Butylcyanoketene with 2′-Cyclohexylspiro [Fluorene-9,3′-Oxaziridine]

Although the reactions of ketenes and three-membered heterocycles containing one hetero atom are well known,^1,2 only one investigation of similar recations with three-membered rings containing two hetero atoms has been reported.³ The reaction of 2-ethyl-3-phenyloxaziridine with diphenylketene was found to afford among other minor products an oxazolidinone derivative (1) and benzaldehyde in yields of 38% and 50% respectively.     

Synthesis of novel spiro-fused pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidines

New pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidines, with an associated spiro-3,3′-oxindole attachment, were prepared by three-component combinations of 5,6-dihydro-4H-pyrrolo[3,2,1-ij]quinoline-1,2-dione with a pair of reactants chosen from a pyrazol-5-one, a pyrazole-5-amine, a barbituric acid, or a 6-aminouracil.     

An Efficient Preparation of 4, 4′-Dicarboxy-2, 2′-Bipyridine

A convenient and high yield preparation of 4, 4′-dicarboxy-2, 2′-bipyridine from the oxidation 4, 4′-dimethyl-2, 2′-bipyridine with potassium dichromate in sulfuric acid is reported.     

Synthesis and reactions of new 4-chloro-2-methylpyrimidino[4′,5′:4,5]thiazolo[3,2-a]-benzimidazoles

Summary 4-Chloro-2-methylpyrimidino[4,5:4,5]thiazolo[3,2-a]benzimidazole (3) was prepared by chlorination of2 which could also be converted directly to 2-methylpyrimidino[4,5:4,5]-thiazolo[3,2-a]benzimidazol-4-thiol (4). Nucleophilic substitution of3 with alcohols, phenols, primary amines, secondary amines, sodium azide, and mercaptoacetic acid gave the corresponding derivatives. The thiol derivative4 was reacted with alkyl/aralkyl halides, phenacyl bromide derivatives, bromoacetone, chloroanilides, bromomalonic ester, and ethyl bromoacetate to afford compounds of potential pharmacological interest.

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Synthese und Reaktionen neuer 4-Chlor-2-methylpyrimidino[4,5:4,5]thiazolo[3,2-a]benzimidazole

Zusammenfassung 4-Chlor-2-methylpyrimidino[4,5:4,5]thiazolo[3,2-a]benzimidazol (3) wurde durch Chlorierung von2, welches auch direkt zu 2-Methylpyrimidino[4,5:5,4]thiazolo[3,2-a]-benzimidazol-4-thiol (4) umgesetzt werden kann, hergestellt. Nucleophile Substitution von3 mit Alkoholen, Phenolen, primären Aminen, sekundären Aminen, Natriumazid und Mercaptoessigsäure ergab die entsprechenden Derivate. Das Thiolderivat4 wurde mit Alkyl/Alkarylhalogeniden, Phenacylbromidderivaten, Bromaceton, Chloraniliden, Brommalonsäureester und Bromessigsäureethylester zu potentiell pharmakologisch interessanten Verbindungen umgesetzt.