2- Adamantyl alcohol

The same Japanese chemists5 found that alcohols are converted in high yield into chlorides by reaction with dichlorocarbene generated in this way. Thus 1-adamantyl alcohol is converted into 1-adamantyl chloride in 94% yield, and benzyl alcohol into benzyl chloride in 90% yield. The reaction proceeds with predominant retention of configuration (SNf). 

A mixture of 1-adamantyl alcohol, aq. 50%-NaOH-soln., and a little benzyltriethyl-ammonium chloride emulsified at 40° by vigorous stirring, chloroform added drop-wise during 2 hrs., and stirring continued 2 hrs. 1-adamantyl chloride. Y ... 

Adamantyl alcohol, 58, 78 2-Adamantyl fluoride, 58, 78 Adipic acid, 56, 70... 

The addition of para-tolylamine to 133 afforded the 1,2-addition complex 142 which was characterised in the solid state confirming the cis orientation of the amide to the newly formed methanide centre. Likewise, reaction of 132 with adamantyl alcohol and 133 with methyl iodide, respectively, afforded the 1,2 addition products 143 and 144. The regioselective nature of these 1,2-additions confirmed the nucleophilic nature of the methandiide centres and this contrasts to electrophilic Fischer carbene centres which are usually attacked by incoming nucleophiles. In contrast, complexes 142-144 are formed by attack of electrophilic centres at the methandiide centres. 

Simple alkanes can be converted to esters with dialkyloxrranes. Cyclic alkanes are oxidized to alcohols with dimethyl dioxirane. " Cyclohexane was converted to cyclohexyl trifluoroacetate with di(trifluoromethyl) dioxrrane and trifluoroacetic anhydride and also with RuCl3/MeC03H/CF3C02H. Dimethyl dioxrrane converts alkanes to alcohols in some cases. Adamantane is converted to adamantyl alcohol with DDQ (p. 1710) and triilic acid. The mechanism of oxygen insertion into alkanes has been examined. ... 

Thermodynamic experimental data for this ion comes from three sources (1) its appearance energy from a variety of precursors (2) the adiabatic ionization energy of the 2-adamantyl radical (3) the DPA study of 2-adamantyl chloride and 2-adamantyl alcohol/ ... 

A very good example of the above behavior occurs with adamantyl containing nucleophiles (adamantyl amine, adamantyl alcohol and adamantyl methanol) [32]. Only partial replacement of chlorine atoms occurs even when the adamantly group is separated from the rest of the molecule by a spacer group (Fig. 3.37). 

On the other hand, the combined use of ZrCU and Nal can be applied for conversion of hydroxy group into iodide as shown in Equation 81 [86]. In refluxing acetonitrile, methoxybenzyl alcohol was smoothly changed into the corresponding iodide. Benzyl alcohol, primary, secondary, ally lie, and adamantyl alcohols were also converted into the corresponding iodides under the same conditions. 

Reaction of dibromocarbene with several adamantyl alcohols has been reported to give the corresponding bromides in low yield [17]. Three such reactions are illustrated in equations 4.9—4.11 [17]. The reaction is analogous to the more thoroughly studied reaction of alcohols with dichlorocarbene (see Sect. 3.3). 

The procedure described here is a modification of one involving the thermal fragmentation of 1-adamantyl hypoiodite and cycliza-tion of the resulting iodo ketone/ By means of this procedure, 4-protoadamantanone is obtained from 1-adamantanol with consistent yields in the range of 71 to 82% and a purity greater than 98%. This method is also applicable to the preparation of other polycyclic ketones from the related bridgehead alcohols with a-bridges of zero, one, or two carbon atoms (see Table I). 

A Strecker p T 43 ) synthesis would require aldehyde (6) which can be made from available alcohol (7). We shall now use R for the adamantyl group. 

Reduction of esters by trichlorosilane in tetrahydrofuran in the presence of tert-butyl peroxide and under ultraviolet irradiation gave predominantly ethers from esters of primary alcohols, while esters of tertiary alcohols were cleaved to acids and hydrocarbons. Esters of secondary alcohols gave mixtures of ethers and acids/hydrocarbons in varying ratios. 1-Adamantyl trimethylacetate, for example, afforded 50-100% yields of mixtures containing 2-42% of 1-adamantyl neopentyl ether and 58-98% of adamantane and trimethylacetic acid [1033]. 

The 2-methyl, 2-cyclopropyl and 2-phenyl substituted 8,9-dehydro-2-adamantyl cations 25 were prepared from their respective alcohols using fluorosulfuric acid in sulfuryl chloride fluoride at low temperatures (equation 27). The relative extent of charge delocalization in these cations was estimated by comparing their NMR spectra. The ions are nonequilibrating static cations, as shown by their proton NMR spectra56. 

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