Trans-Pinocarveol

BASE-INDUCED REARRANGEMENT OF EPOXIDES TO ALLYLIC ALCOHOLS trans-Pinocarveol,... 

Bicyclo[3,l,l]heptanes.—Spin-lattice relaxation time measurements have facilitated the n.m.r. spectral assignments of paeoniflorin and albiflorin (Vol. 3, p. 71). trans-Pinocarveol (223) has been synthesized from /3-pinene in t-butyl alcohol with hydrogen peroxide in the presence of a catalytic amount of selenium... 

R-Me) with none of the well known ring-contracted ketone which is observed in protic solvents (Vol. 2, p. 54 Vol. 4, p. 63 Vol. 5, p. 41). Similar reaction of the isomeric 2a-hydroxy-3/3-tosyloxypinane yields trans-pinocarveol (223 74%) presumably via 2a,3a-epoxypinane (Vol. 6, p. 44). °... 

BASE-INDUCED REARRANGEMENT OF EPOXIDES T 0 ALLYLIC ALCOHOLS trans- PINOCARVEOL... 

Synthetic routes to trans-verbanone are discussed,308 and mercuric acetate in boiling methanol converts /3-pinene into a 65 35 mixture of the myrtenol ether (212 R = Me) and the trans-pinocarveol ether (213 R = Me).309... 

Treatment of the alkenylpotassium (210 X = K) with dimethoxyfluoroborane and peroxide gives (+)-myrtenoI (210 X = OH) contaminated with 2% of trans-pinocarveol (213 R = H).331 Alkylation of the ir-allyl complex (230) occurs directly on carbon from the more hindered side of the molecule to yield (231).332 Heating a-or /3-pinene with pentacarbonyliron yields the chiral ring skeletal enantiomers (232) and (233) by 7r-allyl cyclobutane ring-expansion.333... 

The ready accessibility of a-pinene epoxide (817) is frequently the reason for its use to make other compounds. A most interesting claim is that with 1 mol% of aluminum isopropoxide at 100-120°C, trans-pinocarveol (603) is obtained, while 5 mol% of the reagent at 140-170°C gives pinocamphone (818). Kane et al. have used the pinanyl oxides cis- and trans-S19 (R = K) to open a-pinene epoxide (817). These alkoxides are made from dimethylsulfmylpotassium and dy-pinanol (819, R = H) (the product of autoxidation of pinane cis here means from ci5-pinane, therefore with the rranj-hydroxyl group) and are among the... 

Myrtenol (203 X = CH2OH) may be obtained most efficiently from the more stable secondary allylic alcohol (+)-trans-pinocarveol (30 enantiomer) via bromination with PBra to the rearranged bromide (203 X = CH2Br) [(30) (203 X = CH20H)/85 15] ester thermolysis and isomerization-oxidation were less effective, and the direct acid-catalysed isomerization was not observed. Intramolecular cyclization of (206), which is readily synthesized via trifluoroacetic anhydride cyclization of 4-methylcyclohex-3-enylacetic acid to (186), affords (207) which is cleaved to (208 X = NH2) in a synthesis of ( )-a-... 

Composition Besides the main component 1,8- cineole minor components ate a- pinenes, p-cymol (see cymenes), limonene (see p-menthadienes), and trans-pinocarveol (see pinenols). 

In connection with structure activity relationship studies, Chapuis [40] prepared a series of sandalwood odorant alcohols. In this context, alcohol 181 has been prepared from (+)-trans-pinocarveol 179 in two steps. Accordingly, orthoester rearrangement of alcohol 179 afforded ester 180 which, after the Grignard reaction, gave tertiary alcohol 181 (Scheme 6.27). 

C with agitation and aeration for 4 days yielded camphor (37 ), bomeol (36a ), isobomeol (36b ), a-terpineol (34 ), and P-isopropyl pimelic acid (248 ) (see Figure 14.154). Using modified Czapek-Dox medium and keeping the other conditions the same, the pattern of the metabolic products was dramatically changed. The metabolites were tran -pinocarveol (2 ), myrtenol (S ), a-fenchol (11 ), a-terpineol (34 ), myrtenic acid (7 ), and two unidentified products (see Figure 14.157). 

Transintestinal cholesterol efflux (TICE), 3446 Trans-isomers, 4066, 4069 Transketolase (TKT), 15 Transmembrane proteins, 2471 Trans-pinane, 4098 Trans-pinocarveol, 2984 Transplastomic, 2833 Transporters, extracellular, 1672... 

Several oxygenated derivatives based on pinane have been found to occur in woody parts. For example, myrtenol (100), myrtenal (101) and myrtenic acid (102) have been isolated from wood of Chamaecyparis formosensis. (-)-trans-Pinocarveol (103) is present in American gum turpentine. (+)-c/5 -Verbenol (104), its trans isomer, and (+)-tra/w-verbenone (105) are important components of frankincense from Boswellia cartevii (275 vol. Ill b, c, 296, 379). From the roots of Paeonia albiflora, a few highly oxygenated pinane derivatives (e.g., paeoniflo-rin, 106) have been obtained (223). 

The volatile oil contains predominantly terpene hydrocarbons (especially pinene, di-pentene, limonene, a-thujene, a- and P-phel-landrenes,/)-cymene, myrcene, andterpinene also a-copaene, P-bourbonene, P-ylangene, P-guaiene, tra 5-bergamotene, P-cadinene, humulene, P-caryophyllene, famesene, etc.), with lesser amounts of oxygenated compounds (famesol, bomeol, carvone, trans-pinocarveol, terpinen-4-ol, menthadien-7-ol, verbenone, tra 5-verbenol, bomyl acetate. 

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