α‐Bromierung von 2‐Adamantylisothiocyanat und Folgereaktionen

Abstract

2-Adamantylisothiocyanat (6) reagiert rnit N-Bromsuccinimid photochemisch zum 2-Brom-2-adamantylisothiocyanat (5), welches sich rnit Nucleophilen unter Substitution des Broms oder unter Addition an die Isothiocyanat-Gruppe rnit anschliel3ender oder gleichzeitiger Eliminierung von HBr umsetzt. Mit Thiophenol erhalt man 10, rnit Aminen ungesattigte Thioharnstoffe der Art 11 und 12, rnit Hydrazinen oder Hydroxylaminen Heterocyclen, z.B. 14, 17, 18, und rnit NaN, den Heterocyclus 19, der thermisch leicht zum Cyanimid 20 zerfallt. Mit NH,SCN reagiert 5 zum geminalen Diisothiocyanat 15, welches rnit Aminen unter Addition an eine NCS-Gruppe und Eliminierung von HSCN, z. B. zu 12 + 16 reagiert. or-Bromination of 2-Adamantyl Isothiocyanate and Subsequent ReactionsOn irradiation of 2-adamantyl isothiocyanate (6) in the presence of N-bromosuccinimide 2-bromo-2-adamantyl isothiocyanate (5) is formed, which reacts with nucleophiles with substitution of bromine or addition to the isothiocyanato group with subsequent or simultaneous elimination of HBr. With thiophenol compound 10 is formed, with amines one gets unsaturated thioureas, e. g. 11 and 12, with hydrazines or hydroxylamines heterocycles, e. g. 14, 17, 18, and with NaN, the heterocycle 19, which easily decomposes to the cyanoimide 20 when heated. Compound 5 reacts with NH,SCN to the geminal diisothiocyanate 15, which adds amines only to one isothiocyanate group with elimination of HSCN giving, for instance, 12 + 16.

Spiro compounds containing adamantane and heterocyclic fragments (review)

“…Adamantanespirooxazolidines (CLXXIV) (yields 34-67%) or the oxazoline derivative (CLXXV) (yield 81%) were synthesized in this way: The oxidative cyclization of the ketone semicarbazone (XVI) by the action of lead tetraacetate leads to the spiro compound (CLXXVIII) with a 50% yield [147] 2-Bromo-2-isocyanatoadamantane and 2-bromo-2-isothiocyanatoadamantane (CLXXXIV) react readily with Nmethylhydroxylamine in the presence of triethylamine and form the respective spiro compounds (CLXXXV) (yields 66-92 %) [99,150] …”

“…The reaction of 2-bromo-2-isothiocyanatoadamantane with hydrazine or N,N'-dimethylhydrazine in the presence of triethylamine was used for the production of the spiro compounds (CXVIII) (yield 76-88%) [99]: g__ s R, reaction time, (hi: H, 1; Me, 12 CXVIII When heated, the diazetidines (CXIX) are transformed into the triazolinone derivatives (CXX). (yields 50-73 %).…”

Synthesis and Antimicrobial Activity of Novel Hydrazone and 1,2,4-Triazole-3-thione Derivatives

“…The 1,2,4-triazole-3-thione fragment occurs in the structure of many natural and biologically active compounds [16,17], for example, in bicyclic anxiolytic drugs, estazolam, alprazolam (Scheme 1), in the triptan 5-HT1 agonist (rizatriptan) and in antimicrobial agents based on spiropiperidinyl-1,2,4-triazolidine-3-thione [18][19][20][21][22]. For the synthesis of heterocyclic compounds with antimicrobial activity with a 1,2,4-triazole-3-thione moiety, the reaction of ketones with thiosemicarbazide is used [23][24][25][26][27].…”