Synthesis and thermal transformations of allyl aryl ethers of adamantane series
TL;DR: In this article, the features of thermal transformations of allyl aryl ethers containing bulky adamantane scaffold were investigated and it was found that the composition of the reaction products is largely dependent on temperature, time and nature of the solvent.
Abstract: Allyl aryl ethers of adamantane series were obtained by reacting (E)-1-(adamant-1-yl)-3-bromoprop-1-ene with phenol or ethyl salicylate. The features of thermal transformations of allyl aryl ethers containing bulky adamantane scaffold were investigated. It has been found that the composition of the reaction products is largely dependent on temperature, time and nature of the solvent. When a nucleophilic solvent was used, the reaction proceeded via formal substitution of phenoxy fragment with nucleophilic species prevailing in the reaction medium.
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TL;DR: The nature and composition of the Ritter reaction products of 1]-(1E)-3-bromoprop-1-en-1yl]-adamantane and 1]-3bromophosphamide-1.2.
Abstract: The nature and composition of the Ritter reaction products of 1-[(1E)-3-bromoprop-1-en-1-yl]-adamantane and 1-(3-bromoprop-1-en-2-yl]adamantane are largely determined by the substrate structure, electrophilic medium, and reaction conditions. Possible reaction paths leading to both conventional Ritter reaction products and heterocyclization or skeletal rearrangement products (homoadamantane γ-sultones) are discussed.
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TL;DR: In this article, the acid-catalyzed ring opening of aminomethyloxiranes afforded the first precursory derivatives, adamantane-containing aminohalohydrins.
Abstract: Functionally substituted oxiranes were synthesized by epoxidation of
unsaturated compounds of the adamantane series with m-chloroperoxybenzoic acid. Adamantyl-substituted
epibromohydrins reacted with nitrogen, oxygen, and sulfur nucleophiles to give
only halogen substitution products. 2-(Adamantan-1-yl)-3-hydroxypropanoic acid
was obtained by the reaction of 2-(adamantan-1-yl)-2-(bromomethyl)oxirane with
98% nitric acid. Acid-catalyzed ring opening of aminomethyloxiranes afforded
trifunctional derivatives, adamantane-containing aminohalohydrins. Treatment oftrans-2-(adamantan-1-yl)-2-(phenylsulfanylmethyl)oxirane withn-butyllithium gave rise to a mixture ofZ and E isomers of
1-(adamantan-1-yl)-3-(phenylsulfanyl)prop-2-en-1-ol, whereas trans-2-(adamantan-1-yl)-3-(phenoxylmethyl)oxirane
under similar conditions was converted to (E)-3-(adamantan-1-yl)prop-2-enal.
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365 citations
TL;DR: Six diverse types of chemical transformations were performed in the presence or absence of a SiC heating element at the same reaction temperature but at different microwave power levels, and the measured conversions/yields were similar regardless of whether a heating element was used or not.
Abstract: The use of passive heating elements made out of chemically inert sintered silicon carbide (SiC) allows microwave transparent or poorly absorbing reaction mixtures to be heated under microwave conditions. The cylindrical heating inserts efficiently absorb microwave energy and subsequently transfer the generated thermal energy via conduction phenomena to the reaction mixture. In the case of low to medium microwave absorbing reaction mixtures, the addition of SiC heating elements results in significant reductions (30-70%) in the required microwave power as compared to experiments performed without heating element at the same temperature. The method has been used to probe the influence of microwave power (electromagnetic field strength) on chemical reactions. Six diverse types of chemical transformations were performed in the presence or absence of a SiC heating element at the same reaction temperature but at different microwave power levels. In all six cases, the measured conversions/yields were similar regardless of whether a heating element was used or not. The applied microwave power had no influence on the reaction rate, and only the attained temperature governed the outcome of a specific chemical process under microwave conditions.
119 citations
TL;DR: Alkoxyalkyl esters of cidofovir have substantially greater antiviral activity and selectivity than unmodified CDV against herpesviruses and orthopoxviruses in vitro and CDV analogs having alkyl ethers linked to glycerol or ethanediol linker groups also demonstrated increased activity against CMV.
Abstract: Alkoxyalkyl esters of cidofovir (CDV) have substantially greater antiviral activity and selectivity than unmodified CDV against herpesviruses and orthopoxviruses in vitro. Enhancement of antiviral activity was also noted when cyclic CDV was esterified with alkoxyalkanols. In vitro antiviral activity of the most active analogs against human cytomegalovirus (HCMV) and orthopoxviruses was increased relative to CDV up to 1,000- or 200-fold, respectively. Alkyl chain length and linker structure are important potential modifiers of antiviral activity and selectivity. In this study, we synthesized a series of alkoxyalkyl esters of CDV or cyclic CDV with alkyl chains from 8 to 24 atoms and having linker moieties of glycerol, propanediol, and ethanediol. We also synthesized alkyl esters of CDV which lack the linker to determine if the alkoxyalkyl linker moiety is required for activity. The new compounds were evaluated in vitro against HCMV and murine CMV (MCMV). CDV or cyclic CDV analogs both with and without linker moieties were highly active against HCMV and MCMV, and their activities were strongly dependent on chain length. The most active compounds had 20 atoms esterified to the phosphonate of CDV. Both alkoxypropyl and alkyl esters of CDV provided enhanced antiviral activities against CMV in vitro. Thus, the oxypropyl linker moiety is not required for enhanced activity. CDV analogs having alkyl ethers linked to glycerol or ethanediol linker groups also demonstrated increased activity against CMV.
82 citations
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