The synthesis of the 9-phosphabicyclo[3.3.1]nonanic and 2-phospha-6-oxaadamantanic systems

Electron impact induced fragmentations and rearrangements of aliphatic, heterocyclic phosphine oxides

“…Ethyl-2,2,2-d3 p -toluenesulfonate gave the following NMR spectrum (neat): 6 2.02 (s, 3 H), 3.7 (s,2 H), 7.02 (d, 2 H, J = 8 Hz), 7.47 (d, 2 H, J = 8 Hz). The appropriately deuterium-labeled sample of ethanol (BioRad Laboratories, Richmond, Calif,) (1.42 ml, 0.024 mol) was added over 15 min to an ice-cold, stirred solution of 5.0 g (0.026 mol) of freshly distilled ptoluenesulfonyl chloride in 10 ml of dry pyridine.…”

Heterocyclic studies. 38. Rearrangement of a 9-acyl-1,9-diazabicyclo[4.2.1]nonadienone to a pyrrolo[1,2-b]pyridazinone

“…This method is analogous to that used in the preparation of 2-oxa-2 and 2-phospha-6-oxaadamantanes.3 2-Acetyl-2-aza-6-oxaadamantane was prepared by the steps shown in Scheme I. The parent material in the synthesis, 9-benzyl-9-azabicyclo[3.3.1 ]nonan-3-one (l),4 was prepared by the exothermic addition of benzylamine to cyclooctadienone, as was also found by Bottini;5 consecutive reduction of 1 by LiAlH4 yielded the expected endo alcohol 2,6 from which the benzyl group could be cleaved by hydrogenolysis under acidic conditions to yield endo-9-azabicyclo [3.3.1 ]nonan-3-ol (3) (milder hydrogenation conditions; e.g., hydrogenation in ethanol, at room temperature and 60 psi did not affect the benzyl group). Compound 3 which is a hygroscopic material was identical in all respects with the one described in the literature.7 Attempts to produce the 9-azabicy clo [3.3.1 ]nonan-3-one directly by addition of ammonia to cyclooctadienone failed; the only prod-…”

“…5,6-Bis(methoxycarbonyl)-7-p-bromophenyl-3-methyl-4-phenylpyrrolo [ 1,[2][3][4][5][6]pyridazin-2-one (2a). A. Methanolic Sodium Methoxide.-A 570-mg (1.1 mmol) sample of la was added to a solution of 25 ml of anhydrous methanol containing 0.2 g of sodium methoxide.…”

“…5,6-Bis (methoxycarbonyl )-4,7-diphenyl-3-methylpyrrolo [1,[2][3][4][5][6] pyridazin-2-one (2b).-A solution of 250 mg (0.56 mmol) of lb8 in 8 ml of methanol was treated with 2 ml of 50% sodium methoxide in methanol. After standing for 20 min at room temperature, the solution was acidified with concentrated HC1 and reduced to an oil under reduced pressure.…”

“…Treatment of compound 3 with acetic anhydridepyridine acetylated the amine as well as the hydroxy group to yield endo-9-azabicyclo [3.3.1 ]nonan-3-ol (5) which, on mild basic hydrolysis gave the corresponding alcohol (6).7 (Schotten-Baumann acetylation of 2 which should result in 6 in one step, gave much lower yields due to side reactions.) Treatment of the endo alcohol 6 with lead tetraacetate in boiling benzene,2'3 or better in the presence of Pb(OAc)4 and iodine,8 gave two compounds.…”