2-adamantanol

A 500-ml flask is equipped with a condenser and a magnetic stirrer and charged with 175 ml of water, 18 ml ofTHF, lOg of potassium carbonate, 6.5 g of silver nitrate, and 10 g of 1-bromoadamantane. The mixture is heated in a boiling water bath for 1 hour with stirring, cooled, and the crystallized 1-adamantanol is collected by filtration. It may be purified by dissolving it in THF and diluting the solution with water. The product has mp 289-290°. 

Solvent-grade benzene was dried over sodium wire prior to use. If the benzene is wet, a considerable amount of starting 1-adamantanol remains unreacted owing to hydrolysis of lead tetraacetate. 

The conditions for gas chromatography are given in Note 9. The product was found mainly in fractions 2-20 by the submitters. The first 25-ml. fraction contained considerable amounts of byproducts, while fractions 21 and higher contained 1-adamantanol. The checkers collected 10-ml. fractions with an automatic fraction collector. 

TERTIARY ALCOHOLS FROM HYDROCARBONS BY OZONATION ON SILICA GEL 1-ADAMANTANOL... 

A gas chromatographic analysis by the checkers (see Note 10) on the material in the third crop from one run showed a major peak for 1-adamanttUiol and a second minor peak having an area ca. 12% of that of the major peak. In another run the area of the peak from this by-product in the third crop was less than 2% relative to that of 1-adamantanol. 

A yield of 5.8 g. (877o), m.p. 280-282°, was obtained by the submitters. The infrared spectrum, proton and carbon-13 magnetic resonance spectra, and mass spectrum of the product were identical to those of an authentic sample of 1-adamantanol. A mixed melting point with an authentic sample of 1-adamantanol showed no depression. 

This dry ozonation procedure is a general method for hydrox-ylation of tertiary carbon atoms in saturated compounds (Table 1). The substitution reaction occurs with predominant retention of configuration. Thus cis-decalin gives the cis-l-decalol, whereas cis- and frans-l,4-dimethylcyclohexane afford cis- and trans-1,4-dimethylcyclohexanol, respectively. The amount of epimeric alcohol formed in these ozonation reactions is usually less than 1%. The tertiary alcohols may be further oxidized to diols by repeating the ozonation however, the yields in these reactions are poorer. For instance, 1-adamantanol is oxidized to 1,3-adamantane-diol in 43% yield. Secondary alcohols are converted to the corresponding ketone. This method has been employed for the hydroxylation of tertiary positions in saturated acetates and bromides. 

Adamantanol has been prepared by oxidation of adamantane with peroxyacetic acetic" and by hydrolysis of 1-bromoadamantane with silver nitrate s or hydrochloric acid. ... 

A. endo-7-Iodomethylbicyclo[3.3.1]nonan-3-one. A 2-1., threenecked, round-bottomed flask equipped with an eflicient mechanical stirrer and a reflux condenser is charged with 600 ml. of dry ben2 ene (Note 1). The flask is immersed in a water bath, stirring is initiated, and 58.3 g. (0.132 mole) of lead tetraacetate (Note 2), 37.4 g. (0.147 mole) of iodine, and 10.0 g. (0.066 mole) of 1-adamantanol (Note 3) are added (Note 4). The bath temperature is gradually raised to 80° over a 20-minute period and is then allowed to cool to 70-75°. Stirring is continued for 2 hours at 70-75° (Note 5) and for an additional hour while the mixtiu e is cooled to room temperature. The inorganic salts are filtered and carefully washed with five 50-ml. portions of ethyl ether. The... 

Adamantanol is available from the following three suppliers Aldrich Chemical Company, Inc., Fluka AG, Buchs, Switzerland E. Merck, Darmstadt, Germany. It may also be prepared from adamantane by bromination to 1-bromoadamantane and hydrolysis. Adamantane is sold by the same three suppliers. 

The temperature of the bath should be carefully maintained in this range. At temperatures below 70° the reaction is much slower and increased amounts of unreacted 1-adamantanol will contaminate the product. At temperatures above 75° the amount of tar in the product is increased. 

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). 

Similarly, and in contrast to the behavior of its secondary isomer, 2-adaman-tanol, 1-adamantanol undergoes smooth, quantitative reduction to adamantane in less than an hour at room temperature in dichloromethane solution containing triethylsilane under the catalysis of either free boron trifluoride129 or boron trifluoride etherate (Eq. 13).143... 

Trimethylsilane in pentane is a particularly good system for the TMSI-catalyzed reductive coupling of tertiary alkoxytrimethylsilanes with aldehydes to form sterically crowded tertiary-primary ethers.337 In this way, 1 -(tert-butoxymethyl)-3-methylbenzene is formed in 87% yield (Eq. 184).338 Reaction of terephthaldehyde with two equivalents of the trimethylsilyl ether of 1-adamantanol under these conditions leads to a good yield of the diadamantyl ether of 1,4-benzenedimethanol (Eq. 185).338... 

Synthesis of 1-Adamantanol from Adamantane through Regioselective Hydroxyiation by Streptomyces griseoplanus Cells... 

The procedure is an approach for the synthesis of 1-adamantanol from adamantane by a green bioprocess. 

Ru PW33(0)3j(dmso)] is made from K [ PW 03, ] aqueous cis-RuCl2(dmso) under microwave irradiation IR, and Ru NMR spectra were recorded. With [Ru PW (0)3 (dmso)] 7aq. Na(10 ) cyclo-octene gave suberic acid, while with [Ru PWj 1(0)3, (dmso)] 7aq. Oxone / Bu(HSO )/DCE/50°C ada-mantane gave 1-adamantanol and 1-chloroadamantane as the main products [825]. No information was given on the nature of the effective catalyst - it is likely that some RuO at least would have been generated. 

BTSP-CF3SO3H is an efficient electrophilic oxygenating agent for adamantane and diamantane. With adamantane, the major reaction product is 4-oxahomoadamantane in isolated yield in 79% through a C—C a-bond insertion with very little 1-adamantanol, the C—H insertion product (equations 57 and 58/. In the case of diamantane, two isomeric oxahomodiamantanes were obtained along with two isomeric bridgehead diamantanols corresponding to C—C and C—H a-bond insertions. 

It has been also found that PhIO as an oxidant in the presence of a catalytic amount of sulfonated manganese and iron porphyrin supported on poly(vinylpyridinium) polymers in olefin epoxidation and alkane hydroxylation is a better oxidant than Bu4NHS05 °. Oxidation of adamantane to 1-adamantanol in good yield using BU4NHSO5 and acetone in the presence of aqueous NaHCOs was also reported . ... 

Adsorption of a condensed 1-hydroxy-adamantane layer at the Hg elec-trode/(Na2S04 or NaF) solution interface has been studied as a function of temperature by Stenina et al. [174]. Later, Stenina etal. [175] have determined adsorption parameters and their temperature dependence for a two-dimensional condensation of adamantanol-1 at a mercury electrode in Na2S04 solutions. They have also studied coadsorption of halide (F , Cl , Br ) anions and 1-adamantanol molecules on Hg electrode [176]. More recently, Stenina etal. [177] have described a new type of an adsorption layer comprising organic molecules of a cage structure condensed at the electrode/solution interface. This phenomenon was discovered for adsorption of cubane derivatives at mercury electrode. 

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