Synthesis and properties of (<Emphasis Type="Italic">E</Emphasis>)-4-[alkyl(aryl)iminomethyl]-2-methoxy(ethoxy)phenyl adamantane-1-carboxylates

Condensation of 4-formyl-2-methoxy(ethoxy)phenyl adamantane-1-carboxylates with aliphatic, cycloaliphatic, and aromatic amines gave the corresponding adamantane-containing Schiff bases as E isomers with respect to the CH=N azomethine bond. The reaction of 2-methoxy-4-(naphthalen-2-yliminomethyl)phenyl adamantane-1-carboxylate with cyclohexane-1,3-dione and dimedone led to the formation of 2-methoxy-4-(11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)phenyl adamantane-1-carboxylates. Quantum-chemical calculations of the energies of formation of E and Z isomers of some of the synthesized Schiff bases were performed.     

Synthesis,molecular structure,conformation and biological activity of Ad-substituted N-aryl-tetraoxaspiroalkanes

An efficient method has been developed for the synthesis of 7′-arylspiro{adamantane-[2,3′]-(1′,2′,4′,5′,7′-tetraoxazocanes)} by the ring transformation reaction of spiro{adamantane-[2,3’]-(1′,2′,4′,5′,7′-pentaoxacane)} with arylamines in the presence of Sm(NO₃)₃·6H₂O as the catalyst. NMR signals of the synthesized compounds were assigned considering the conformation dynamics of the tetraoxazocane ring with two rigid peroxide bonds. The structures of some of the compounds were studied by X-ray diffraction. The thermal stability of single crystal was determined by DSC method. Compounds 7′-(2-methylphenyl)spiro{adamantane-[2,3′]-(1′,2′,4′,5′,7′-tetraoxazocane)} and 7′-(4-fluorophenyl)spiro{adamantane-[2,3′]-(1′,2′,4′,5′,7′-tetraoxazocane)} exhibited cytotoxicity towards cancer cells.     

Synthesis and structure of (trichlorogermyl)methyl adamantane-1-carboxylate

The reaction of adamantane-1-carboxylic acid chloride with trichlorogermylmethanol afforded (trichlorogermyl)methyl adamantane-1-carboxylate, whose molecular structure was established by ¹H NMR spectroscopy and X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1576–1579, July, 2005.     

Adamantane and its derivatives. 1. Hydrazones and pyrazolones of adamantane

The dihydrazones, bis(diphenylhydrazones), and bis (2,4-dinitrophenylhydrazones) of adamantanone-2-carboxylic acid, dimethyl adamantane-2,6-dione-1,5-dicarboxylate, and tetramethyl adamantane-2,6-dione-1,3,5,7-tetracarboxylate and the pyrazolones of the corresponding acids were synthesized. It is shown that the methyl esters of adamantane-2,6-dione-1,5-dicarboxylic and -1,3,5,7-tetracarboxylic acids and their hydrazones cannot be converted to adamantane-1,5-dicarboxylic and -1,3,5,7-tetracarboxylic acids under the conditions of the Huang-Minlon and Locke reactions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 528–531, April, 1982.     

Arylation of adamantanamines: III. Palladium-catalyzed arylation of adamantane-1,3-diyldimethanamine and 2,2′-(adamantane-1,3-diyl)diethanamine

Palladium-catalyzed arylation of adamantane-1,3-diyldimethanamine and 2,2′-(adamantane-1,3-diyl) diethanamine with isomeric bromochloro- and dibromobenzenes was studied. The yields of N,N′-diarylation products depend on the initial diamine and dihalobenzene structure. Side reactions were revealed, which reduced the yield of the target products. The arylation of 2,2′-(adamantane-1,3-diyl)diethanamine gives the corresponding N,N′-diaryl derivatives with better yield. The possibility for synthesizing unsymmetrical N,N′-diaryl derivatives of 2,2′-(adamantane-1,3-diyl)diethanamine was demonstrated.     

Reactions of methyl esters of adamantane acids with acetonitrile

Russian Chemical Bulletin - Methyl adamantane-1-carboxylate and methyl (1-adamantyl)acetate react with acetonitrile in the presence of sodium hydride to give 3-(1-adamantyl)-3-oxopropanenitrile and...     

1H NMR studies of maltose,maltoheptaose, alpha-, beta-, and gamma-cyclodextrins,and complexes in aqueous solutions with hydroxy protons as structural probes

The (1)H NMR chemical shifts, coupling constants, temperature coefficients, and exchange rates have been measured for the hydroxy protons of aqueous solutions of alpha-, beta-, and gamma-cyclodextrins, maltose, and maltoheptaose. In cyclodextrins (CDs), the high chemical shift of the O(3)H signal and its small (3)J(OH,CH) value suggest that O(3)H is involved in a hydrogen bond. The small temperature coefficients and rate of exchange values of O(2)H and O(3)H confirm the involvement of O(3)H in hydrogen bonding and indicate that O(2)H is the hydrogen bond partner. In maltose, two distinct NMR signals with two different vicinal coupling constants are found for O(2')H. A cross-peak in the ROESY spectrum indicates chemical exchange between the O(2')H and O(3)H protons. The existence of two distinct NMR signals with different J values for O(2')H shows the influence of anomeric configuration on the O(2')H-O(3)H interaction. The effect of complexation with methyl benzoate, adamantane-1-carboxylic acid, adamantane-1-ol, and l- and d-tryptophane on the NMR spectra of the hydroxy protons of alpha-, beta-, and gamma-cyclodextrins and of maltose has been investigated. No significant spectral changes were observed upon addition of methyl benzoate and adamantane-1-carboxylic acid. The addition of adamantane-1-ol resulted in an upfield shift and a strong broadening of the O(2)H signal from alpha-CD, and a small temperature coefficient was measured upon complexation. The O(2)H and O(3)H signals in beta-CD were broadened and shifted downfield upon addition of l- and d-tryptophane.     

Reaction of thioketones with propiolic acids

The reaction of adamantane-2-thione with propiolic acid afforded a novel type of cycloadduct, spiro[adamantane-2,2'-6'H-[1,3]-oxathiin]-6'-one (3a), in quantitative yield. The reaction of thiobenzophenone with propiolic acid gave 2,2-diphenyl-6'H-[1,3]-oxathiin]-6'-one and 4-phenyl-3-thia-3,4-dihydronaphthoic acid in 34% and 35% yields, respectively. The reaction might proceed through a concerted process, as confirmed by kinetics. The reaction of adamantane-2-thione with 2-butynoic acid or phenylpropiolic acid gave the corresponding adducts regioselectively. Interestingly, only one isomer was obtained by the reaction of thiofenchone with propiolic acid, suggesting that the reaction proceeded diastereospecifically. Oxidation of adducts by dimethyldioxirane or m-chloroperoxybenzoic acid gave the corresponding sulfoxides and sulfones. The sulfoxides were thermally decomposed to give disulfide or another type of 1,3-oxathiin-6-one.     

Synthesis of adamantane and bicyclo[3.3.1]nonane derivatives with the oxetane moiety

A method of synthesis of 3-hydroxyoxetane esters with adamantane- and bicyclo[3.3.1]nonane-containing carboxylic acids is reported.     

Synthesis of Thione-Propiolic Acid Adducts

Abstract

Reaction of adamantane-2-thione with propiolic acid gave a novel type of cycloadducts, spiro[adamantane-2,2′-(1,3)-oxathiin]6-one, quantitatively. Thiocamphor and thiofenchone also reacted with propiolic acid to give the corresponding adducts stereoselectively. The observation of second-order reaction kinetics and highly stereoselective addition strongly support a cycloaddition mechanism for the thermal addition. The reaction of selenoketones with propiolic acid afforded a similar cylcoadduct. This is the first example of the reaction of monomeric thiones or selones with acetylenic acids.     

Reactions of 1,3-dehydroadamantane with inorganic oxygen-free acids

A convenient and efficient procedure has been developed for the synthesis of 1-azidoadamantane, 1-adamantyl isocyanate, and 1-adamantyl isothiocyanate by reaction of 1,3-dehydroadamantane with hydrazoic, isocyanic, and isothiocyanic acids, respectively, under mild conditions. The reaction of 1,3-dehydroadamantane with hydrogen cyanide under analogous conditions gives adamantane-1-carbonitrile in a poor yield which may be improved using hexane as solvent.     

Synthesis and properties of azoles and their derivatives

Thermal condensation of 1-cyanoadamantane with arylhydroxamic acid chlorides gave 5-(1′-adamantyl)-1,2,4-oxadiazoles containing aromatic groupings in the 3 position. The same 1,2,4-oxadiazoles were synthesized by reaction of the N-oxides of the appropriate nitriles with adamantane-1-carboxylic acid methyl imino ester obtained from 1-cyanoadamantane. The corresponding 5-(1′-adamantyl)-3-substituted 1,2,4-oxadiazoles were obtained by condensation of the latter with amidoxines.     

Preparation of 1-aminomethylenemercapto derivatives of 2, 4, 6, 8-tetrathiaadamantane and adamantane

1-Aminomethylenemercapto derivatives of 3, 5, 7, 9, 9-pentamethyl-2, 4, 6, 8-tetrathiaadamantane and adamantane were obtained by aminomethylation of 3, 5, 7, 9, 9-pentamethyl-2, 4, 6, 8-tetrathiaadamantane-l-thiol and adamantane-1-thiol.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 658–660, May, 1976.     

Oxydation chromique de l'adamantanone : preparation de l'acetoxy-5 adamantanone-2

chromic oxidation of adamantanone gives adamantane-2,6-dione (20%), 5-hydroxy adamantan-2-one (6%) and 5-acetoxy adamantan-2-one (36%).     

Synthesis and properties of azoles and their derivatives

The corresponding mono- and bisheterocyclic derivatives of adamantane were obtained by reaction of the dinitrile or diimino ester of adamantane-1,3-dicarboxylic acid with ethylenediamine and related compounds.See [1] for communication XXIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1654–1657, December, 1976.     

Synthesis of (3-Hydroxyadamantan-1-yl)methanols

A convenient procedure has been developed for the synthesis of (3-hydroxyadamantan-1-yl)-methanols on the basis of nitroxylation of adamantan-1-ylmethanols with fuming nitring acid and subsequent reduction of intermediate nitric acid esters with hydrazine hydrate. The title diols have also been obtained by the reduction of 1-nitroxy-3-(nitroxymethyl)adamantanes. The nitroxylation process is accompanied by oxidation with the formation of substituted adamantane-1-carboxylic acids.     

Palladium-catalyzed amination in the synthesis of macrocyclic compounds containing 1,3-disubstituted adamantane fragments

Palladium-catalyzed amination of 1,3-dibromobenzene, 2,6-dibromopyridine, 3,3′-dibromobiphenyl, 2,7-dibromonaphthalene, and 1,8-dichloroanthracene with an equimolar amount of 2,2′-(adamantane-1,3-diyl)diethanamine resulted in the formation of macrocyclic compounds containing one or several adamantane and one or several aromatic fragments. The reactions of 2,2′-(adamantane-1,3-diyl)diethanamine with excess 1,3-dibromobenzene, 2,6-dibromopyridine, 1,8-dichloroanthracene, and 1,8-dichloroanthraquinone gave the corresponding N,N′-diaryl derivatives. Polyaza macrocycles incorporating adamantane, aromatic, and 4,7,10-trioxatridecane-1,13-diamine fragments, were obtained by palladium-catalyzed amination of the N,N′-diaryl derivatives with 4,7,10-trioxatridecane-1,13-diamine.     

Efficient Catalytic Synthesis of α,ω-Di(spiro[adamantane2,3′-[1,2,4,5,7]tetroxazocan]-7′-yl)alkanes

Russian Journal of Organic Chemistry - An efficient method has been developed for the synthesis of α,ω-di(spiro[adamantane-2,3′[1,2, 4,5,7]tetroxazocan]-7′-yl)alkanes by...     

Cu<Superscript>I</Superscript>-catalyzed <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>’-diarylation of diamines of adamantane series

A copper(I) complex-catalyzed N,N’-diarylation of diamines based on 1,3-disubstituted adamantane, using aryl iodides bearing electron-donating and electron-withdrawing substituents, was studied. In the case of 2,2’-(adamantane-1,3-diyl)ethanediamine, the optimal catalyst system is CuI—2-(isobutyryl)cyclohexanone—Cs₂CO₃—DMF. The highest yield of diarylation product was reached in the case of 4-methoxyiodobenzene (79%). In the case of more spatially hindered adamantane-1,3-diyldimethanamine, 1,1’-binaphthalene-2,2’-diol (BINOL) should be used, with the highest yield of the target product (84%) being reached in the reaction with iodobenzene.     

The use of 1H and 13C spin-lattice relaxation rates in the structure determination of adducts of adamantane-1-carbonitrile and lanthanide chelates in solution; comparison with the results of measurements of lanthanide induced shifts

Gd(fod)₃ induced enhancements of ¹H and ¹³ spin-lattice relaxation rates showed the Gd-N distance in adducts of Gd(fod)₃ and adamantane-1-carbonitrile to be 2.60 Å. A good estimate of the intermolecular contribution to the enhancement of the relaxation appears to be essential in this method of structural analysis. The results of this investigation are compared with those of calculations based on lanthanide induced shifts.