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Upstream product

• 768-93-4 1-iodoadamantane 
• 88377-60-0 α-methylacetophenone anion 
• 93-55-0 1-phenyl-propan-1-one 

Relevant academic research and scientific papers

The Photostimulated Reaction of 1-Iodoadamantane with Carbanionic Nucleophiles in DMSO by the SRN1 Mechanism

1-Iodoadamantane (1) reacts under irradiation with the enolate ions of acetone (2), acetophenone (5a), and propiophenone (5b) to give adamantane and the substitution products in variable yields.The anion of nitromethane (7) does not react under irradiation with 1, but excellent yields of 1-adamantylnitromethane (8) are obtained in the photostimulated reaction of 1 and 7 in the presence of 2 or 5a (entrainment reactions).We suggest that 1-iodoadamantane reacts with these nucleophiles by the SRN1 mechanism of nucleophilic substitution.

Carbon-carbon bond formation by radical addition-fragmentation reactions of O-alkylated enols

α-tert-Butoxystyrene [H2C = C(OBut)Ph] reacts with α-bromocarbonyl or α-bromosulfonyl compounds [R 1R2C(Br)EWG; EWG = -C(O)X or -S(O2)X] to bring about replacement of the bromine atom by the phenacyl group and give R 1R2C(EWG)CH2C(O)Ph. These reactions take place in refluxing benzene or cyclohexane with dilauroyl peroxide or azobis(isobutyronitrile) as initiator and proceed by a radical-chain mechanism that involves addition of the relatively electrophilic radical R 1R2(EWG)C* to the styrene. This is followed by β-scission of the derived α-tert-butoxybenzylic adduct radical to give But*, which then abstracts bromine from the organic halide to complete the chain. α-1-Adamantoxystyrene reacts similarly with R 1R2C(Br)EWG, at higher temperature in refluxing octane using dα-tert-amyl peroxide as initiator, and gives phenacylation products in generally higher yields than are obtained using α-tert-butoxystyrene. Simple iodoalkanes, which afford relatively nucleophilic alkyl radicals, can also be successfully phenacylated using α-1-adamantoxystyrene. O-Alkyl O-(tert-butyldimethylsilyl) ketene acetals H2C=C(OR)OTBS, in which R is a secondary or tertiary alkyl group, react in an analogous fashion with organic halides of the type R1R2C(Br)EWG to give the carboxymethylation products R1R2C(EWG)CH 2CO2Me, after conversion of the first-formed silyl ester to the corresponding methyl ester. The silyl ketene acetals also undergo radical-chain reactions with electron-poor alkenes to bring about alkylation-carboxymethylation of the latter. For example, phenyl vinyl sulfone reacts with H2C=C(OBut)OTBS to afford Bu tCH2CH(SO2Ph)CH2CO2Me via an initial silyl ester. In a more complex chain reaction, involving rapid ring opening of the cyclopropyldimethylcarbinyl radical, the ketene acetal H 2C=C(OCMe2C3H5-cyclo)OTBS reacts with two molecules of N-methyl- or N-phenyl-maleimide to bring about [3 + 2] annulation of one molecule of the maleimide, and then to link the bicyclic moiety thus formed to the second molecule of the maleimide via an alkylation-carboxymethylation reaction.

Catalyzed Reactions of Enol Ethers with SN1 Active Groups: A Novel Method for the Preparation of α-Alkylated Ketones

The performance of tert-alkylations, alkoxyalkylations, and aldehyde enolate allylations proceeding with low catalyst loading (0.1 mol % - 5 mol %) is described. The reactions are complete within short times and can even be performed without solvent and under ambient conditions. The mechanism of the reaction was investigated by deuterium labeling and cross-over studies.

Reactivity of 1-Iodoadamantane with Carbanions by the SRN1 Mechanism

The photostimulated reaction of 1-iodoadamantane (1) with carbanions in DMSO has been studied.Acetone enolate ion (2a) reacted with 1 to give the substitution product (4a, 20percent) and adamantane (3, 17percent); acetophenone enolate ion (2b) gave the substitution product (4b, 65percent) in the presence of 18-crown-6.In the reaction with propiophenone enolate ion (2c), the yield was lower (27percent).Anthrone anion (5) gave good yields (75percent) of the substitution product 6.The anion of nitromethane (7) did not react with 1 under photostimulation, but in the presence of 2a or b, 87percent of 1-adamantylnitromethane (8) was obtained (entrainment reactions).Low amounts of substitution products were found with the fluorene anion and no substitution was observed with other carbanions.It is suggested that these reactions occurred by the SRN1 mechanism.By competition experiments, the following reactivity order toward 1-adamantyl radicals was determined: 2a (1.0) a of the conjugate acid of the anions and on the changes in ? energy (HOMO carbanion - SOMO radical anion intermediate) that takes place in the coupling reaction.By competition experiments of 1 and PhI toward 2b, a k1:KPhI ratio of ca. 16 was found while 1-bromoadamantane and PhBr gave a k1-BrAd:kPhBr ratio of ca. 0.13.This difference can be attributed to the capacity of phenyl radicals to abstract iodine atoms from 1 giving PhI and 1-adamantyl radicals, which ultimately results in an apparent greater reactivity of 1 vs.PhI.