Alkylation of aromatic compounds with adamantan-1-ol

Reactions of substituted benzenes, naphthalenes, and 2- and 3-phenyl-1-benzofurans with adamantan-1-ol in trifluoroacetic acid lead to the formation of the corresponding mono-and diadamantylsubstituted aromatic compounds.     

Adamantylazoles: X. Reactions of 1,2,4-Triazole-3-thione with 1-Adamantanol in Acid Solutions

1,2,4-Triazole-3-thione reacts with 1-adamantanol in concentrated sulfuric acid to form 1-(1-adamantyl)-1,2,4-triazole-3-thione, which transforms into 1-(1-adamantyl)-3-(1-adamantyl)sulfanyl-1,2,4-triazole or is oxidized with atmospheric oxygen dissolved in sulfuric acid into 3,3′-disulfanediylbis[1-(1-adamantyl)- 1,2,4-triazole]. 3-(1-Adamantyl)sulfanyl-1,2,4-triazole was prepared by adamantylation of 1,2,4-triazole-3-thione in a mixture of phosphoric and acetic acid (weight ratio 4 : 1).     

Adamantylazoles: IX. Acid-catalyzed Adamantylation of 1,2,4-Triazol-3-thione

1,2,4-Triazole-3-thione reacts with 1-adamantanol in sulfuric acid to form 1-(1-adamantyl)-3- [(1-adamantyl)sulfanyl]-1,2,4-triazole and 3,3′-disulfandiylbis[1-(1-adamantyl)-1,2,4-triazole].__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 142–145.Original Russian Text Copyright © 2005 by Amandurdyev, Saraev, Polyakova, Golod.     

Adamantylazoles: XIII. Specificity of acid-catalyzed alkylation of 1-(1-adamantyl)-4,5-dihydro-1H-tetrazole-5-thione

Russian Journal of General Chemistry - In the reaction of 1-(1-adamantyl)-4,5-dihydro-1H-tetrazole-5-thione with 1-adamantyl in sulfuric acid 2-(1-adamantyl)-5-(1-adamantylsulfanyl)-2H-tetrazole...     

Reaction of ethylene oxide with n-phenylated isomers of 1,2,4-triazoline-3-thione and 1-phenyltetrazoline-5-thione

It is demonstrated that ethylene oxide forms N--hydroxyethyl derivatives of the corresponding triazolin-3-ones in the reaction with 1-phenyl- and 4-phenyl-1,2,4-triazolin-3-thiones and with 3--hydroxyethylthio derivatives of 1-phenyl- and 4-phenyl-1,2,4-triazole in acetic acid. 1-Phenyltetrazolin-5-thione reacts similarly with ethylene oxide. Under the influence of ethylene oxide, 2-methyl-4-phenyl-1,2,4-triazolin-3-thione is converted to 2-methyl-4-phenyl-1,2,4-triazolin-3-one.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 700–703, May, 1971.     

Adamantylazoles: XII. Alkylation of 1-R-tetrazole-5-thiones and 1-R-tetrazol-5-ones with tertiary alcohols in sulfuric acid

In the reaction of 1-(1-adamantyl)-4,5-dihydro-1H-tetrazole-5-thione with 1-adamantyl in sulfuric acid 2-(1-adamantyl)-5-(1-adamantylsulfanyl)-2H-tetrazole and 1,3-bis(1-adamantyl)-5-(1-adamantylsulfanyl)-1H-tetrazolium salt are formed. Methylation of 1-(1-adamantyl)-4,5-dihydro-1H-tetrazole-5-thione in alkaline medium affords 1-(1-adamantyl)-5-methylsulfanyl-1H-tetrazole while its interaction with formaldehyde affoeds 1-(1-adamanttl)-4-(hydroxymethyl)-4,5-dihydro-1H-tetrazole-5-thione.     

Adamantylazoles: XIV. Acid-catalyzed alkylation of 5-aminotetrazoles with tertiary alcohols

Alkylation of 5-aminotetrazole with tert-butyl alcohol or adamantan-1-ol in sulfuric acid gave a mixture of isomeric N ¹- and N ²-alkyl derivatives, as well as 1,3-dialkyl-5-aminotetrazolium salt. Adamantylation of 1-substituted 5-aminotetrazoles led to the formation of mixtures of 1,3- and 1,4-disubstituted 5-aminotetrazolium salts which can be converted into the corresponding free bases.     

Adamantylazoles. 5. The molecular structure of 1-(1-adamantyl)pyrazoles

The crystal structures of 1-(1-adamantyl)-3,5-dimethylpyrazole 1 and 1-(1-adamantyl)-3,4,5-trimethylpyrazole 2 were studied by X-ray analysis. The space groups and cell parameters are: 1 , Cc, 13.4452(4), 14.9407(4), 7.1119(2) Å, 90, 111.944(2), 90°, with Z = 4. 2, P2₁/c, 6.7466(1), 21.2565(7), 10.1462(2) Å, 90, 106.368(2), 90°, with Z = 4. The final disagreement factors were 0.069 and 0.061, for 721 [2σ(I)] and 1950 [2σ(I)] observed reflexions, respectively. Compound 1 presents the adamantyl residue disordered between the two usual conformations. The experimental dipole moments and the carbon-13 chemical shifts (both in hexadeuteriodi-methylsulfoxide and in the solid state) were measured and discussed in connection with the structure of these compounds.     

Reaction of 5-methyl-1,3,4-thiadiazoline-2-thione with molecular iodine

Russian Chemical Bulletin - The formation of the n-σ* complex of 5-methyl-1,3,4-thiadiazoline-2-thione with molecular iodine of the composition C3H4N2S2·I2 in dilute chloroform solutions...     

Adamantylazoles: VIII. Acid-catalyzed adamantylation of 1,2,4-triazol-5-ones

3-R-1,2,4-Triazol-5-ones are adamantylated in sulfuric acid. The reaction involves the N¹ atom of the ring. 4-Adamantyl-1-methyl-, 1-adamantyl-4-methyl-, and 1,4-diadamantyl-1,2,4-triazol-5-ones were also prepared. Therewith, it was found that N¹ exhibits a higher reactivity than N⁴.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1377–1382.Original Russian Text Copyright © 2004 by Amandurdyeva, Saraev, Kuzmina, Golod.For communication VII, see [1].This revised version was published online in April 2005 with a corrected cover date.     

Reaction of adamantan-2-amine and (adamantan-1-yl)methylamine with methyl 2-(4-allyl-2-methoxyphenoxy)acetate

A reaction of methyl 2-(4-allyl-2-methoxyphenoxy)acetate with adamantan-2-amine and (adamantan-1-yl)methylamine in butanol leads, together with the target amides, to the formation of butyl ester of the corresponding acid, which is resistant to aminolysis.     

Reaction of pyridine-2-thione with acetylenes

In contrast to 2-pyridone, pyridine-2-thione reacts with acetylene with the participation of one reaction center — the sulfur atom. The reaction with phenylacetylene and diacetylene proceeds stereospecifically to give products with cis structures. The structures of the synthesized compounds were confirmed by chemical and spectroscopic methods.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 364–367, March, 1978.     

Kinetic studies of the copper-catalyzed cross-coupling of 1-phenyltetrazole-5-thiol and iodobenzene

Kinetics of the copper-catalyzed cross-coupling of 1-phenyltetrazole-5-thiol and iodobenzene under thermal and dielectric heating has been studied; the kinetic parameters of the reaction have been calculated. Microwave irradiation has not influenced significantly the reaction molecular mechanism; the process acceleration can be due to macrokinetic effects.     

Reaction of benzimidazole-2-thione with 1,2-dibromoethane. Coronand synthesis

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, p. 136, January, 1990.     

Reaction of 1,2,4-triazole-3-thione with acetylene

A mixture of 1,2,4-triazol-3-yl vinyl sulfide and N,S-divinyl derivatives is formed in the reaction of 1,2,4-triazole-3-thione with acetylene under pressure. The mixture of N,S-divinyl derivatives was separated into two isomers by gas-liquid chromatography. The hydrogenation, polymerization, and complexing of 1,2,4-triazol-3-yl vinyl sulfide were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1561–1563, November, 1977.     

Reaction of benzimidazole-2-thione with cyanoacetylene alcohols

Conclusions 2-Iminobenzimidazo-1,3-thiazines containing a hydroxyl group were obtained by the reaction of benzimid-azole-2-thione with tertiary cyanoacetylene alcohols. It was observed that they have enhanced stability toward alkalis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1903–1904, 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.     

Heterocyclization of quinazol-2-ylguanidines. 1. Reaction with amino acids

Condensation of 6(7)-R-4-methylquinazol-2-ylguanidines with -amino acids produces 2-hydroxyimidazoles; with anthranilic acid, the corresponding 4-hydroxyquinazolines.Voronezh State University, Voronezh 394693, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 934–936, July, 1999.