Zur Kenntniss des Carvons

Abstract

Die weitere Untersuchung der Titantartrate und ahnlicher Verbindungen, rnit der ich beschiiftigt bin, so11 besonders auf das Studium des Temperatureinflusses :tuf die Drehung ausgede!int werden.Wisserischaftlich-chern. Laborat. R e r l i n N., Schiittelt man Carvon rnit Schwefelsaure, so lagert sich W a s s e r an, und es entsteht ein O x y d i h y d r o c a r v o n . Beim Reduciren rnit Natrium uud Alkohol erhalt mau daraus ein gesattigtes Dihydroxylderivat, und dieser Eiirper ist zweifellos ideutisch rnit dem von B a e y e r und H e n r i c h I) BUS dem Broiriwasserstoffadditionsproducte (11) des Dihydrocarveols (I) dargestellteu Dihydrocarveolglykol (111) (durch Behandeln des Bromides rnit Silberacetat u. s. w.), sodase unserem Oxydibydrocarvon die Formel eines 8-0 x y -8.9 -d i h p d r oc a r v o n e s (IV)zukommt.

Oxymercuration of 2,6-Dimethylhepten-5-ol-2

“…The volatile oil was identified as 2,2,6,6-tetramethyltetrahydropyran by preparation of its hydrogen bromide addition product, which was identical with that obtained from the authentic material (15). The reduction product obtained by treatment of 2,6-dimethyl-3-iodomercuriheptanediol-2,6 (II, X = iodide) with hydrazine hydrate is not a known substance.…”

“…65-66°was formed. This melting point was not depressed upon admixture with the hydrogen bromide addition complex formed from authentic 2,2,6,6-tetramethyltetrahydropyran prenared from 2,6-dimethylheptanediol-2,6 (15). 2-[2,2-DimelhyUetrahydrofuryl]propanol-2.…”

Pinol derivatives from lithium aluminum hydride reduction of cineole chlorohydrin

“…An analytical sample of 4 was obtained by GLC and showed IR and NMR spectra identical with those of al- A solution of 55 mg of 1 and 29 mg of a 57% mineral oil dispersion of sodium hydride was heated at reflux in THF for 25 h. The mixture was cooled, neutralized with dilute hydrochloric acid, and extracted with ether. The ether solution was dried (MgS04) and carefully evaporated to give 45 mg of pinol oxide (6) which was homogeneous according to GLC analysis on a 10% Carbowax column. cis-Dihydropinol (9).…”

“…The tertiary alcohol 4 was characterized by its NMR spectrum which showed, in part, methyl singlets at 1.23 and 1.37 ppm and a one-proton doublet at 3.82 ppm attributed to the bridgehead hydrogen of a pinol derivative. The structure of 4 was confirmed by comparison with an authentic sample prepared by lithium aluminum hydride reduction of (±)-pinol oxide (6) Complete characterization of 2 was not possible because of a lack of sufficient material. However, its infrared spectrum in solution showed hydroxyl absorption at 2.78 and 2.89 µ, while its CAT improved NMR spectrum displayed methyl singlets at 1.14,1.27, and 1.34 plicity are consistent with the assignment of an exo proton at C-6 in an oxabicyclo[2.2.2]octane ring system.…”

“…The first step in the reduction of 1 must involve the -reaction of the alcohol group to afford intermediate 13. Ionization of chloride, possibly assisted by an electrophilic aluminum species and/or neighboring oxygen, generates cation 14 (or its classical counterparts). The cation may be attacked by hydride, most likely in an intramolecular fashion,7 to yield alcohol 5, or by oxygen at C-6 to give pinol oxide (6), which is then reduced by lithium aluminum hydride to alcohol 4. In connection with the latter conversion it is instructive to note that pinol oxide ( 6) is formed in high yield when cineole chlorohydrin (1) is treated with sodium hydroxide2 or sodium hydride.…”