Ketone adamantyl methyl

Vinyl cations also have been invoked as intermediates in the addition of carbonium ions generated in strong acid to acetylene (50-53). Sasaki et al (50) observed 1-adamantyl methyl ketone, 25, as the sole product in the reaction of acetylene with 1-bromoadamantane in concentrated H2SO4 at 5°. Bott (51), on the other hand, reported a mixture consisting of 75% 1-adamantylacetaldehyde,... 

C12H17NO 4-benzyl-4-hydroxypiperidine 51135-96-7 551.15 48.820 2 24450 C12H180 1-adamantyl methyl ketone 1660-04-4 524.28 46.221 2... 

The first attempt to imprint a metal complex with a reaction intermediate coordinated to the metal center was reported by Mosbach and coworkers [51], A Co monomer coordinated with dibenzoylmethane, which is as an intermediate for the aldol condensation of acetophenone and benzaldehyde, was tethered to a styrene-DVB copolymer matrix. After, the template, dibenzoylmethane was removed from the polymer, the resulting molecularly imprinted cavity had a shape similar to the template due to the interaction of the template with the polymerized styrene-DVB monomers through n-n stacking and van der Waals interactions. The rate of aldol condensation of adamantyl methyl ketone and 9-acetylanthracene was lower than the rate of condensation with acetophenone, indicating some degree of increased substrate selectivity. This is the first known formation of a C-C bond using a molecularly imprinted catalytic material. 

Other studies of electrophilic additions to acetylenes include the reaction of tribenzylaluminium with acetylene the reaction of phthalic anhydride with ynamines to give indanediones or benzoxepinones the reaction of adamantan-l-ol with acetylene in 98 % sulphuric acid leading to adamantane-aldehyde and adamantyl methyl ketone and the effects of organosilicon substituents on the properties of a triple bond. "... 

In parallel studies the reactions of acetylene in sulphuric acid with adamantan-1-oP - and with methyladamantanols have been examined. Products and probable intermediates are shown in Scheme 25. Adamantyl methyl ketone is only obtained if a good nucleophile can intercept the cation before the fast ring-expansion can occur. 

For example, acetyladamantane and isopropyl methyl ketone gave 1-adamantyl-acetamide in 85% yield and N-acetyl-isopropylamine in 46% yield, respectively [79]. A similar a-cleavage was observed in the electrochemical oxidation of the a-branched cyclic ketone (43) using Et3N-5HF as an electrolyte (Scheme 16) [81]. 

In this section we are considering cyclic ketones in which the >CO group is not part of the ring. The two compounds of greatest interest here are 1-adamantyl methyl ketone120 (51a) and bis(l-adamantyl)ketone121 (51b) with their respective gas-phase enthalpies of formation of —298.3 3.2 and —367.8 5.0 kJmol-1. Abboud and coworkers121 considered formal reaction 42... 

In parallel with these studies, other ligands were assessed for use in sodium-selective electrodes, including the methyl, butyl, and adamantyl ketone tetramers of p-f-butylcalix[4]arene. However, only the methyl ketone derivative produced satisfactory PVC membrane electrodes [6]. These were subsequently applied to the analysis of sodium in plasma samples [11]. Excellent correlations (r = 0.979, r = 0.987 and r = 0.951, n = 10) were found in comparative tests with three reference... 

Treatment of 1-bromoadamantane with AlBr3 in the presence of ethylene at -75 °C to give l-(j3-bromoethyl)-adamantane 202) followed by reduction 20°) results in good yields of 1-ethyladamantane (Eq. (63)). Wolf-Kishner 164) or Clemensen 203) reduction of commercially available methyl adamantyl ketone provides an alternative route for the preparation of this compound. 

When radical pairs are produced by a cleavage of ketones, and the loss of CO is prevented on energetic grounds, fragments of the reactions of the primary radical pair become important. Deoxybenzoins (15)30) or adamantyl ketones (20)25,30) provide examples of such systems. The photodecomposition of l,2-diphenyl-2-methyl-pro-panone (15)30) illustrates an example of a photofragmentation in reaction (Scheme VIII). The ratio of the major products are highly dependent on solvent environment. For example, the photochemistry of this compound in acetonitrile or benzene yields... 

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