Myrtanol

The adsorptive separation of pinenes on Zeolites is reported.303 The C-6 and C-7 13C n.m.r. chemical shifts in bicyclo[3,l,l]heptanes support other known conformational evidence and confirm that cls-pinane and ds-myrtanol (209 X = OH) have a bridged-boat conformation, that trans-myrtanol has a bridged-chair conformation, and that trans-2-pinanol and myrtenol (210 X = OH) have Y-shaped conformations verbenone (211 R R2 = O), and trans-verbenol (211 R1 = H, R2 = OH) give anomalous results which may be due to a conjugation effect the bridged-chair... 

Athene —r alcohol The reagent prepared from SnCla (1 equiv.) and NaBH (4 equiv.) in THF reacts with olefins to afford anti-Markownikoff alcohols after aqueous work-up. Examples include 2-phenylpropane-l-ol (58%) from a-methyl-styrene, isopinocampheol (40%) from a-pinene, cw-myrtanol (43%) from / -pinene, 1,2-diphenylethanol (53%) from frans-stilbene, and 1-hydroxy-acenaphthene (60%, together with acenapthene, 15%) from acenaphthylene. The reaction with dienes such as limonene and 1,5-cycIooctadiene gave complicated results. The mechanism of this hydroxylation is uncertain. 

Papers of no great novelty concern the attempted synthesis of isopinothiocam-phone [c/5-(210 R = Me, X = S)], lead oxide oxidation of /S-pinene, peroxidation of a-pinene over glass wool, the formation of 2a,3a-epoxypinane and hydration into sobrerol, reduction of chrysanthenone (187), the stereospecific chlorohydroboration-oxidation of /S-pinene to c/s-myrtanol and of a-pinene to (216 X = OH), and the conversion of nopinone into [3- H]myrtenal. ... 

The chiral oxime ethers can be synthesized from the oxime and chiral halides or tosylates. The chiral halides and tosylates were obtained from ( —)-ris-myrtanol, (S)-proline. (S)-valine, (S)-leucine, or (S)-alanine. 

Incorporation of a chiral chain in the Schiff-base ligand led to the formation of a chiral crystal H phase, Cr 107.2 H 148.9 I and Cr 113 H 132.3 I, for both complexes 104b bearing the citronellol or the 2-octanol chain (104b R = OR ), respectively recall that both imine ligands exhibited a SmC phase (Cr 50.4 SmC 77.3 I and Cr 47 SmC" 48 I). In this case, the N,N-trans N,N-cis ratio was 9 1. Ligands and complexes with bulky chiral chains like (—l-rw-myrtanol or (—(-menthol were not liquid crystalline. 

FIGURE UJ.struc The structure of trans-myrtanol (with numbering). 

I FIGURE U.7.gcosy The 2-D H- H gCOSY NMR spectrum of fraro-myrtanol in CDCI3. 

FIGURE 12.7The2-D H- C gHSQC NMR spectrum of fraro-myrtanol inCDCIj. 

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