Zur Kenntnis der Bestandteile ätherischer Öle (Über die Konstitution von Camphen: Seine Oxydation mit Ozon.)

Abstract

Iiisher niclits Sicheres I)eknnnt, i3t. Uas Gyc1:iniiii besitzt :irif Crrintl tler Rlenieiitarannlyse etwn die Formel (C, Ha O)x ; tlie Forniel cleh Kotiiplexes mug dann (c:, 113 O), + C?, H46 0 sein; die Analyse des Atlditionsprodiiktes ist nur init der Vorniel ( ( : I 113 0 ) l e + C2i 1146 0 oder triit einer selir iihnlichen Forniel vereiubar. Das Cyclainin iiiiinte also etwa die Forinel C 3 6 1 1 5 , o l s (oder besser &H56 0 1 s ) und der Koniples et\v:i tlie Forniel CG:) 11102 0 1 9 besitzeu; fiir diese Formel herechnen sich C 65.02, H 5.84.

Reaction of 2-norbornyl- and 3,3-dimethyl-2-norbornylmagnesium bromide with acetone

“…The preparation of camphenilone (6) has been reported by other workers. 7 The procedure described here provides a product of substantially improved purity with a considerable reduction in effort. The reduction of camphenilone with Spectra were recorded at 100 MHz in CC14 containing -1:1 (molar) Eu(fod)3:endo-l. Coupling constants (J) are in hertz.…”

“…6 Strong coupling was observed between H, and H2x but its magnitude could not be accurately determined because of overlapping interference from H7. MgBr 9 L1AIH4 is sterospecific,8 insofar as can be determined by 1H NMR analysis, producing only endo-3,3-dimethylnorbornan-2-ol (endo-camphenilol, 7). The conversion of 7 to its tosylate 8 was achieved by conventional procedures and requires no additional comment.…”

The Ozonolysis of Terpenoids, a Pandora's Box of by-Products

“…An early example was the formation of the lactone 32 as well as the anticipated ketone 31 in the ozonolysis of the sterically hindered alkene of camphene 30. 55,56 Other more recent examples have been observed in ozonolysis of β-pinene to give nopinone, 57 and of ent-kaur-16-ene 58 as well as the kaurenolides, 59 which gave lactones as by-products during the preparation of the nor-ketones.…”

Untitled

“…The first decade of the century saw the establishment of the structures of further monoterpenes such as the αand β-phellandrenes 12 and 13, 16 sabinene 14, 17 fenchone 15 and camphene 16 18 whilst the stereochemical relationships between geraniol, nerol and the citrals a and b were elucidated. 19 An important facet of this work involved the unambiguous synthesis of the oxidative degradation products of the terpenes such as camphoric acid 11, 20 α-campholactone, 21 terpenylic 7 and homoterpenylic acids 17.…”