The Structure and Reactions of the 1: 1 Adduct of Benzenesulfonyl Azide and Bicyclo[2.2.1]heptene

Heteroatom participation during addition-rearrangement reactions of 2-thia- and 2-azanorbornenes

“…F. l,4-DiphenyI-3-(hexafluoroisopropylidene)-2-thiabicyclo[2.2.1]hept-5-ene (16). 1,4-Diphenylcyclopentadiene38 (6.72 g, 0.03 mol), 25 ml of hexane, and 7.56 g (0.04 mol) of bis(trifluoromethyl)thioketene3S were refluxed for 16 hr.…”

“…The third cut was recrystallized twice from hexane to yield 4.23 g (12%) of 7-bromo-6-tertbutoxy-3-(hexafluoroisopropylidene)-2-thiabicyclo[2.2.1]heptane: mp 56-56.5°; nmr (CCI4) 1.15 [s, (CH3)3C], 2.25 (m, CH2), 3.42 (s, 1-H), 3.74 (4-H, broadened by F), 4.12 (m, 6-H), 4.25 38.14; H, 3.56; Br, 19.27. C. anti -7-Bromo-4,6-diphenyl-3-(hexafluoroisopropylidene)-2-thiabicyclo[2.2.1 ]hept-5-ene (19). 16 (4.12 g, 0.01 mol) was dissolved in 15 ml of dichloromethane, cooled, and stirred in ice, and 3.30 g (0.0105 mol) of tetramethylammonium tribromide40 was added in portions. Bromination followed by spontaneous dehydrobromination took place rapidly.…”

“…1,4-Dihydro-l,4-methanopyridazino[1,2-6]phthalazine-6,-11-dione29 was prepared by the reaction of cyclopentadiene, 1,2-dihydro -1,4-phthalazinedione, and lead tetraacetate in dichloromethane46 and recrystallized from nitromethane: 78%; mp 238-239°. To a stirred solution of 6.78 g (0.03 mol) of the dione in 170 ml of dichloromethane in a flask wrapped with aluminum foil was added 4.80 g of bromine and the solution was allowed to stand for 16 hr. The solvent was removed and the residue was rinsed with acetone and recrystallized from nitromethane to give 9.7 g (84%) of the dibromide, mp 248-251°dec.…”

“…A solution of 13.5 g (0.05 mol) of diphenyl diazodicarboxylate47 dissolved in 50 ml of dichloromethane was stirred and cooled in ice while 3.3 g (0.05 mol) of cyclopentadiene was added. The solution was allowed to stand at 24°for 16 hr and then evaporated. The residue, 15.9 g (95%), was recrystallized from carbon tetrachloride to give 13.8 g (82%), mp 112-114°.…”

Fluorocyclopropanes. III. 1,4-Cycloaddition reactions of perfluorocyclopropene and 1,2-bis(trifluoromethyl)-3,3-difluorocyclopropene

“…difluoro-8-oxatricyclo[3.2.1.02'4]oct-6-ene (9) with 2. Quadricyclane and 2 gave 3,5-bis(trifluoromethyl)-4,4-difluorotetracyclo[5.2.1.02'6.03i6]dec-8-ene (10); with 1 the product was 3,4,5,5-tetrafluorotricyclo[5.2.1.02-6]deca-3,8-diene (11), presumably resulting from cyclopropylallyl rearrangement of the intermediate tetracycle corresponding to 10. Norbornadiene and 1 gave 4,5,5,6-tetrafluoropentacyclo[5.3.0.0 2•10.0 3•8.04• 6]decane (12) which underwent cyclopropyl-allyl rearrangement to 4,4,5,6-tetrafluorotetracyclo[5.3.0.02 10.03'8]dec-5-ene (13). With 2 the product was 4,6-bis(trifluoromethyl)-5,5-difluoropentacyclo[5.3.0.02• 10.03'8.04'e]decane (14).…”