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Pre-extracted radial sections of southern yellow pine sapwood were treated with CCA-C and analyzed by x-ray photoelectron spectroscopy (xps). The ratio of C1 (carbon bonded only to carbon andor hydrogen) to C2 (carbon bonded to one oxygen with a single bond) was used to determine the progress of oxidation of wood components during CCA fixation. This ratio increased after treating times of 10 minutes and 60 minutes and decreased after 180 minutes soaking suggesting that oxidation of C2 predominates on initial contact with CCA solution but oxidation of C1 (lignin) becomes more important with extended exposure to the treating solution. Oxidation ofC2 to C3 (carbon bonded to two oxygens or a carbonyl group) was demonstrated by in situ trapping of C3 with ethylene glycol as it was formed. Further oxidation of C3 to C4 (carboxylic carbon) was not observed in the xps spectra, consistent with the findings of others. The hypothesis that rapid decarboxylation results in loss of C4 as evolved CO, is supported by the observation that the C4 component of untreated wood was reduced by more than 90 % after 10 minutes of CCA soaking followed by high temperature fixation and by the observation of CO, evolution during early stages of accelerated fixation. The Cr(2p) spectra of Crm and C p were established at 580.2 and 577.8 eV respectively. Accelerated fixation of CCA-C treated specimens resulted in a very high degree of reduction of C r " ' to C P . X P S Cu (2p3/2) peaks were established at 935.1 for CCA-C, 935.3 for Cu(OH),, and 933.7 for CuO. Cu (2p3/2) peaks in CCA-treated wood were shown at 932.9 with no satellite peaks for the 10-60 minutes soaking in CCA series, and at 933.9 and 936.4 w i t h satellite at 941-948 for the 3 hours soaking time. The latter are attributed 53 54 KALDAS, COOPER, AND SODHI t o complexed copper oxide and hydroxide forms of Cu'. Peaks attributed to Cu' hydroxides were shown to diminish in leached samples.

Dedicated to Professor Zdetzek (Denny) Valetzta otz the occasion of his 65th birthday PETER YATES and MACDY KALDAS. Can. J . Chem. 70, 1492Chem. 70, (1992. Treatment of 2-norobornene-1-carboxylic acid (7) with one equivalent of methyllithium in ether followed by a second molar equivalent after dilution with tetrahydrofuran gave 1-(norborn-2-en-1yl)ethanone (10) and only a trace of the tertiary alcohol 11. Reaction of 7 with formic acid followed by hydrolysis gave a 4 : 3 mixture of e-ro-3-and exo-2-hydroxynorbornane-1-carboxylic acid (16 and 17), whereas oxymercuration-demercuration gave only the exo-3-hydroxy isomer 16. Oxidation of 16 and 17 gave 3-and 2-oxonorbomane-1-carboxylic acid (27 and 29), respectively. Oxymercuration-demercuration of 10 gave exclusively 1-(exo-3-hydroxynorborn-1 -yl)ethanone (30), which was also prepared by treatment of 16 with methyllithium in analogous fashion to that used for the conversion of 7 to 10. Oxidation of 30 gave 1 -(3-oxonorbom-1 -yl)ethanone (1). Dehydrobromination of exo-2-bromonorbornane-1 -acetic acid and dehydration of 2-hydroxy-norbornane-2-acetic acid derivatives gave 1 -(norborn-2-y1idene)acetic acid derivatives to the exclusion of norbom-2-ene-1-acetic acid derivatives. Treatment of exo-5-acetyloxy-2-norobornanone (52) with ethyl bromoacetate and zinc gave ethyl exo-5-acetyloxy-2-hydroxynorbornane-exo-and etzdo-2-acetate (53 and 54). Reaction of 5 3 with hydrogen bromide gave initially ethyl endo-3-acetyloxy-exo-6-bromonorbomane-1-acetate (59), which was subsequently converted to a mixture of 5 9 and its exo-3-acetyloxy epimer 61. Catalytic hydrogenation of this mixture gave a mixture of ethyl endo-and exo-3-acetyloxynorbomane-1-acetate (62 and 63). Basic hydrolysis of this gave a mixture of the corresponding hydroxy acids, 70 and 71; the former was slowly converted to the latter at pH 5. Oxidation of the mixture of 70 and 71 gave 3-oxonorbornane-1-acetic acid (72). Treatment of the mixture with methyllithium as for 1 6 gave a mixture of 1-(endo-and exo-3-hydroxynorborn-1-y1)-2-propanone (73 and 74), which was oxidized to 1-(3-0x0-norborn-1-y1)-2-propanone (2). Reaction of exo-2-hydroxynorbornane-1-acetic acid lactone (75) with methyllithium in ether gave (1-(exo-2-hydroxynorbom-1-y1)-2-propanone (76), which on oxidation gave the 2-0x0 isomer 78 of 2.PETER YATES et MACDY KALDAS. Can. J. Chem. 70, 1492Chem. 70, (1992. Le traitement de l'acide norborn-2-he-1-carboxylique (7) par un Cquivalent de mkthyllithium dans l'kther, suivi par un deuxikme equivalent molaire aprks dilution avec du tktrahydrofurane, fournit de la 1-(norborn-2-&n-1-yl) Cthanone (10) et que des traces de l'alcool tertiaire 11. La rCaction du produit 7 avec de l'acide formique, suivie d'une hydrolyse, foumit un mklange 4 : 3 des acides exo-3-et e.ro-2-hydroxynorbornane-1-carboxyliques (16 et 17) propan-2-one (2). Le reaction de la lactone de l'acide exo-2-hydroxynorbornane-1 -acCtique (75) avec du mCthyllithium dans 1'Cther donne de la 1-(exo-2-hydroxynorborn-I-yl) propan-2-one (76), qui pa...

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Rearrangements in the Acid-Catalyzed Formation of Lactones from 2-Hydroxynorbornane-2-acetic Acid Derivatives and Related Compounds. -Mechanisms are proposed for the formation of the lactones that involve protonation and carbocation formation followed by Wagner-Meerwein rearrangement, endo-6,2-hydride and exo-3,2-hydride shifts. -(YATES, P.; KALDAS, M.; Can.