Hydroxymethyl cyclohexanols

NUCLEOPHILIC HYDROXYMETHYLATION OF CARBONYL COMPOUNDS 1-(HYDROXYMETHYL)CYCLOHEXANOL (Cyclohexanemethanol, 1 -hydroxy )... 

This procedure for the preparation of 1 -(hydroxymethyl)cyclohexanol is a modification of that reported by the submitters.4 While 1 -(hydroxymethyl)cyclohexanol has been conventionally prepared from methylenecyclohexane by dihydro xylation53 or from cyclohexanone in three steps through the cyanohydrin,5b the present method consists of an alternative route from cyclohexanone via nucleophilic hydroxymethylation. 

In a study related to the conformational properties of the cyclohexane-fused six-membered heterocycles, new bicyclic dithiolanes, 285-/ra r (Scheme 52) and 285-crr (not shown), were prepared along the reaction pathway, as precursors used further for the syntheses of 2-methyl substituted and unsubstituted /ra r-fused 4a,5,6,7,8,8a-hexahydro-2//,4//-1,3-benzodithiines, exemplified by structure 288-/ra ir (R=R = H) <2002JOC1910>. Thus, ditosylation of cis-Z-hydroxymethyl cyclohexanol 284, and subsequent reaction with sodium sulfide and sulfur, provided a mixture of new bicyclic products 285 and 286, albeit in very low yields, with configurational inversion at C-1. These were reduced by LiAlH4 to provide /ra r-2-mercaptomethyl cyclohexanethiol 2 l-trans. Upon acetalization or transacetalization, the desired 2SS-trans derivative was obtained. The same methodology with the precursor 2E4-trans was extended to the preparation of the r-fused bicyclic compounds 285-288. 

Nucleophilic Hydroxymethylation of Carbonyl Compounds 1-(Hydroxymethyl )cyclohexanol... 

Polyols with a large number of terminal hydroxyl groups result when the reaction is initiated with compounds such as pentaerythritol, 2,2,6,6-tetrakis(hydroxymethyl) cyclohexanol, or with natural products, for example, sucrose, raffinose, or D-mannitol. Amines such as ethylenediamine, diethylenetriamine, and 2,4-diaminotoluene may also be used as the active hydrogen-containing initiator. 

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