Reaction of ethyl 3-(1-adamantyl)-3-oxopropanoate with fluorobenzoyl chlorides

Russian Journal of Organic Chemistry -     

New synthesis of 4-(1-adamantyl)-2-aryl-1,3-thiazoles from 4-(1-adamantyl)-1,2,3-thiadiazole

Treatment of 4-(1-adamantyl)-1,2,3-thiadiazole with potassium tert-butoxide generated potassium 2-(1-adamantyl)ethynethiolate which reacted with aromatic carboxylic acid chlorides to give unstable S-[2-(1-adamantyl)ethynyl] arenecarbothioates whose acid hydrolysis afforded S-[2-(1-adamantyl)-2-oxoethyl] arenecarbothioates. The latter reacted with ammonium acetate in acetic acid yielding 4-(1-adamantyl)-2-aryl-1,3-thiadiazoles. Reactions of 4-(1-adamantyl)-2-(4-chloro-3-nitrophenyl)-1,3-thiadiazole with cyclic secondary amines gave the corresponding products of nucleophilic replacement of the chlorine atom in the aromatic ring.     

Thermolysis of 3-(1-adamantyl)-2-hydroxy-5-methylbenzyl-(trimethyl)ammonium iodide

Russian Journal of Organic Chemistry -     

Synthesis of 5(6)-(1-adamantyl)benzimidazoles

New 2-alkyl and 2-aryl derivatives of 5(6)-(1-adamantyl)benzimidazole have been synthesized. Certain reactions of N-alkylation and N-acylation of these compounds have been studied.     

Halogenation and nitrosation of 2-(1-adamantyl)indolizine

Russian Journal of Organic Chemistry -     

New method for preparing 5(6)-(1-adamantyl)-benzimidazole

I. Dzhavakhishvili Tbilisi State University, Tbilisi 380028. Georgia State Zootechnical and Veterinary Educational and Research Institute, Tbilisi 38017. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, p. 843, June, 1994. Original article submitted June 7, 1994.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-[4-hydroxy(alkoxy,acyloxy)-3-alkoxy-benzylidene]-1-(1-adamantyl)ethanamines from 1-(1-adamantyl)ethanamine hydrochloride (Rimantadine)

Reactions of 1-(1-adamantyl)ethanamine with vanillin, vanillal, veratraldehyde, 3-ethoxy-4-methoxybenzaldehyde, and 4-formyl-2-methoxy(ethoxy)phenyl esters gave previously unknown Schiff bases containing an adamantane fragment.     

Reaction of potassium 2-(1-adamantyl)ethynethiolate with nitrilimines

Russian Journal of Organic Chemistry -     

Synthesis and reactions of some 5(6)-(1-adamantyl)benzimidazoles

4-(1-Adamantyl)-1,2-diaminobenzene, previously unreported in the literature, has been prepared and a novel series of 5(6)-(1-adamantyl)benzimidazole derivatives synthesized. Nitration, hydrogenation, and side chain reactions have been carried out. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1172–1182, August, 2008.     

Synthesis of amino acid derivatives of 4-(1-adamantyl)benzoic acid obtained by transition metal ion catalyzed oxidation of 4-(1-adamantyl)toluene

An efficient synthesis of 4-(1-adamantyl)benzoic acid based on transition metal ion catalyzed oxidation of 4-(1-adamantyl)toluene has been developed. As a catalytic system, cobalt-manganese bromide with addition of manganese acetate was used. A series of amino acid derivatives of 4-(1-adamantyl)benzoic acid was then synthesized and characterized. These derivatives are novel intermediates potentially useful in the design of therapeutically active peptidomimetics with improved pharmacokinetic and pharmacodynamic parameters.     

A short-cut from 1-acetyl adamantane to 2-(1-adamantyl)pyrroles

The oxime of 1-acetyl adamantane 2 is added to acetylene (KOH/DMSO, 70 °C, initial acetylene pressure 13 atm, 30 min) to afford the corresponding O-vinyl oxime 5 in 80% yield. The latter upon heating (DMSO, 120 °C, 1 h) gives 2-(1-adamantyl)pyrrole 3, 1-acetyl adamantane 1, and adamantane (6:3:1 mass ratio), the yield of the pyrrole 3 being 83% (based on 1-acetyl adamantane 1 consumed). Under harsher conditions (NaOH/DMSO, 130 °C, atmospheric pressure of acetylene, 4 h) oxime 2 reacts with acetylene to furnish pyrrole 3, 1-acetyl adamantane 1, 1-vinyl adamantane 9, and adamantane (6:7:3:1 mass ratio), with the isolated yield of pyrrole 3 reaching 34%. Under pressure (NaOH/DMSO, 120 °C, initial acetylene pressure 14 atm, 1 h) the same reaction leads to 2-(1-adamantyl)-1-vinylpyrrole 4 and ketone 1 in 48% (based on consumed ketone 1) and 24% yields, respectively. The pyrrole 4 is easily deprotected to the corresponding 1H-pyrrole 3 in 77% yield by treatment (aqueous MeCN) with Hg(OAc)₂ and NaBH₄.     

Synthesis of functionalized 5-(3-R-1-adamantyl)uracils and related compounds

Efficient synthetic approaches to functionalized 5-(3-R-1-adamantyl)uracils and related compounds (R=OH, COOH, NH₂, etc.) are described. The selective hydroxylation of the adamantane tertiary C-H bonds in 5-(1-adamantyl)uracils with H₂SO₄ in trifluoroacetic anhydride is used as the key step. Subsequent electrophilic reactions of 5-(3-hydroxy-1-adamantyl)uracils with N- and C-nucleophiles in CF₃COOH, H₂SO₄ or H₂SO₄/AcOH media yielded derivatives with amide, amino, aryl, carboxy and thiourea groups in the adamantane core. The preliminary evaluation of the antiviral activity revealed that some of the synthesized species display moderate antiviral activity against HSV-1 (SI∼20) in Vero cells.