Synthese und Reaktionen von ?-Campholenverbindungen

Abstract

Synthesis and Reactions of β‐Campholene Compounds In contrast to the well known α‐campholenic (B) and fencholenic compounds (C) little is known about β‐campholenic derivatives (A) because of their difficult accessibilitiy. β‐Campholenic compounds (A) can be obtained: (1) by Baeyer‐Villiger oxidation of camphor via lactone 7 and β‐dihydrocampholenic lactone (5); (2) by Beckmann fragmentation of camphor oxime via α‐(2) and β‐campholenic nitril (3) and the lactone 5; and (3) by acid catalysed rearrangement of α‐campholenic derivatives (B, 17a, b). The β‐analogous brahmanol (14) can be synthesized by the reaction of the β‐campholenic bromide (11) with methyl diethyl malonate or by rearrangement of brahmanol.

Synthesis of Deuterium‐Labeled Perfume Ingredients as Internal Standards for Their GC/MS Quantification

“…2, 3,4,5,6,7,8,9,10,11,12, )methyl]-1H-cyclopenta [12]annulene (¼ 2,3,4,5,6,7,8,9,10,11,12, )methyl]-1H-cyclopentacyclododecene; 28). A suspension of 27 (110 mg, 0.505 mmol) and Lindlar catalyst (5.5 mg) in AcOEt (10 ml) was hydrogenated (11.3 ml of H 2 ) in 30 min.…”

“…4, 5,6,7,8,9,10,11,12, )methyl]-1H-cyclopenta [12]annulene (¼ 4,5,6,7,8,9,10,11,12, )methyl]-1H-cyclopentacyclododecene; 27). A soln.…”

“…), 237 (12), 255 (35), 219 (8), 212 (10), 198 (38), 158 (10), 145 (25), 129 (21), 114 (37), 100 (62), 88 (61), 72 (100), 55 (74), 41 (57). 14-[( 2 H 3 )Methyl]bicyclo [9.4.0]pentadec-1(11)-en-12-one (¼ 2, 3,4,5,6,7,8,9,10,11,12, )methyl]-1H-benzocycloundecen-1-one; 30a). A soln.…”

“…We chose Dartanol as a first example of a sandalwood-like alcohol [7] (Scheme 3). The unreported a-dideuterated campholenal intermediate (þ)-9b [7] 6 ), was obtained in 77% yield from (þ)-9a by exchange with D 2 O/pyridine [8].…”

“…The unreported a-dideuterated campholenal intermediate (þ)-9b [7] 6 ), was obtained in 77% yield from (þ)-9a by exchange with D 2 O/pyridine [8]. Subsequent condensation (Na, D 2 O, MeOD, yield 24%) with 2.0 mol-equiv.…”