Trans 1-Decalol

Double bonds further removed from the incipient carbocation than the homoallylic position can also assist, in jonizatien-if the..geometry of the system. allows Tt. For example -nitrobenzoate (59) solvolyzes 1500 times faster than the corresponding saturated compound in aqueous acetone. The product is trans,trans-1 -decalol (60). If after 12 half-lives the product is iso-... 

Optical resolution of trans-1 -decalol, trans-2 -decalol has been carried out and conversions into trans-decalones of high optical purity have been effected. trans-syn-trans-Perhydroanthracen-2. -ol was also resolved and converted into the ketone. 

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. 

Hydroxylation Perbenzoic acid (C6H6, 100°) can effect hydroxylation of hydrocarbons with a regioselectivity of 60-90% in favor of formation of tertiary alcohols. This reaction involves radicals since it is inhibited by hydroquinone. The hydroxylation of cis-and trans-decalin is stereoselective thus the former is converted mainly into cw-9-decalol (97 3) and the latter is converted mainly trans-9-decalol (95 5). 

Decalin. Decalin was chosen to study the reactivities and selectivities of and a-(5 disubstituted cyclohexane ring as well as the influence of the adjonction of a second saturated Cf, ring. The cis- and trans-isomers were photoxidized in the same conditions. The cis-isomer was found at least 10 times more reactive with a selectivity of 81% in mild oxidation products and 19% in CO2. The following relative selectivities for the main mild oxidation products (2-decalone, with small amounts of 1-decalone and 2-decalol (decahydro-2-naphtol) were found ... 

Hydrogenation of franr-2-decalone (23) with a fixed conformation gave trans,trans-2-decalol (the axial alcohol) in a high stereoselectivity of 98% both with rhodium catalyst in THF-HC1 and with platinum catalyst in AcOH-HBr. On the other hand, the hydrogenation stereochemistry of cis-2-decalone (24) is complicated by the two interconvertible conformations as shown in Scheme 5.9. A mixture of 66% cis,trans and 34% cis,cis isomers was obtained over rhodium in THF-HC1. Similarly, a mixture of 44% cis,trans and 56% cis,cis isomers was produced over platinum in AcOH-HBr.163... 

Decalol, dehydration, 50, 92 Dewar benzene, 50,51 trans-1,8-Diacetoxybicyclo [4.2.0 ] octa-2,4-diene, 50,24 trans, [Pg.57]

Among the non-steroidal alcohols applied to the Oppenauer oxidation are the cis and trans a-decalols (14), which give excellent yields of the corresponding a-decalones (IS).22 Oxidation of phenolic compounds bearing pendent aliphatic secondary alcohols can be readily performed without prior protection of the phenolic alcohol functionality.23 Acid-sensitive acetal 16 is smoothly converted to the corresponding ketone 17, by exploiting a modified experimental procedure.3,24... 

The importance of coplanarity of the eliminating fragments is emphasised by the large difference in the Arrhenius activation energies for elimination from cw-4-r-butylcyclohexanol (E (cis) = 21 kcal.mole" ) and rra/iJ-4-r-butylcyclo-hexanol (Epitrans) = 38 kcal.mole ) . In the trans isomer, elimination must occur from a diequatorial syn-clinal conformation, or a diaxial conformation with the bulky r-butyl substituent in an unfavourable axial conformation, or an initial epimerisation to the cis isomer, or via a boat conformation, all possibilities which involve much higher energy intermediates than the diaxial elimination from the cis isomer. The products of elimination from the four stereoisomers of 1-decalol are also consistent with anti stereospecificity ... 

Since traus-decalin is achiral, the rotations of the decalols serve as a measure of the change in molecular rotation to be expected on insertion of a hydroxy group in other compounds containing trans-fusQd cyclohexane rings. The two possible equatorial... 

Decahydro-P-naphthol CAS 825-51-4 EINECS/ELINCS 212-545-3 Synonyms Decahydro-2-naphthol cis-trans-Decahydro-p-naphthol trans-Decahydro-2-naphthol trans-Decahydro-p-naphthol Decahydro-2-naphthol, mixt. of isomers 2-Decalinol 2-Decalol 2-Hydroxydecalin Naphthalen-2-ol, decahydro- 2-Naphthalenol, decahydro-... 

The four isomeric [l,l,4,4- H4]3-dimethylamino-trans-2-decalols have been synthesized in order to investigate their conformations. Where the amino-function is axial and the hydroxy equatorial, /h-2—h-3 = spectral measurements... 

Gerber, N. N. Geosmin, from Microorganisms, is trans-, 0-T> vQQihy -trans-9 decalol. Tetrahedron Letters 1968, 2971. 

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