Reactive intermediates in the bicyclo[3.1.0]hexyl and bicyclo[3.1.0]hexylidene systems. IV. Free-radical chlorination and chloroformylation of bicyclo[3.1.0]hexane

Reactions of bicyclo[2.1.0]pentane and bicyclo[4.1.0]heptane with hydrogen chloride. Cleavage of cyclopropane rings

“…In addition II was reacted with a twofold excess of anhydrous HC1 in a glass ampoule, filled on a vacuum line, sealed, and heated (10) J. D. " Same reaction run in the dark. 6 An additional component here is toluene which accounts for 13% of the olefin fraction. The relative percentages of the three olefins are calculated after toluene is subtracted out and represent 87% of the olefin fraction.…”

“…A. Tobias, ibid., 89, 6651 (1967), and earlier papers; (b) A. C. Cope and G. L. Woo, ibid., 85, 3601 (1963). (6) (a) R. J, Ouellette, A. South, Jr., and D. L. Shaw, ibid., 87, 2602 action has been discussed in terms of polarization of the three-membered ring by the incoming electrophile.…”

“…The nmr spectrum exhibited two S-methyl peaks at r 7.94 and 8.02 with a relative ratio of 80:20. With this accurate lead, the composition of the 59% component was determined to be a mixture of ¿rcros-2-methylthiobicyclo [3.1.0 [hexane (5) and frans-3-methylthiobicyclo [3.1.0 [hexane (6), with the trans-2 thio ether present as the major component, by preparation of authentic standards and infrared spectral comparison.…”

Radical chlorination of exo- and endo-tricyclo[3.2.1.02,4]octane and exo,exo- and exo,endo-tetracyclo[3.3.1.02,4.06,8]nonane with tert-butyl hypochlorite

“…Our initial attempt at the synthesis of 1 was thwarted by the apparent rearrangement of 1 to 2.2 We have subsequently shown that 1 can be detected by the treatment of the endoier?-butyldimethylsiloxynorborn-5-en-2-one and other difficultly hydrolyzed derivatives of 3-hydroxynorborn-5-en-2one with base and DMSO or by electrolysis of the diketone in the esr cavity.3 The esr spectra of 1 indicated that perla (oH in G) haps 15% of the unpaired electron is transferred by delocalization to the vinyl bridge, a result in agreement with the photoelectron spectrum of norbornadiene4 or norbornenone. 5 We now present evidence concerning the mechanism and the scope of the rearrangement of 1 to 2 which is formally a 1,3-sigmatropic rearrangement.…”

Two novel routes to spiro[3.4]octan-1-ones

“…Our previous experience included decomposition of lactone tosylhydrazone salts (9) Characterization data are given below: 1, ir 1775 cm-1 (vs); nmr (220 MHz) 5 1.14 (s, 6 ), 1.36-1.81 (m, 8 H), 2.66 (s, 2 H); 2, 1775 cm"1 (vs); nmr (220 MHz) 0.927 (d, / = 5 Hz) and 0.955 (d, / = 5 Hz) (6 ), 1.36-2.08 (m, 10 ), 2.60 8 Hz, 1 H); 9a, ir 1780 cm"1 (vs); nmr (220 MHz) 1.09 (s, 6 ), 1.55-2.04 (m, 8 H), 2.26 (s, 2 H); 10a, ir 1780 cm-1 (vs); nmr (220 MHz) 0.945 (d, / = 7 Hz) and 0.950 (d, J = 7 Hz) (6 ), 1.55-2.03 (m, 9 ), 2.03-2.27 (m, 2 H), 2.36-2.59 (m, 1 H); 9c, ir 3200, 1680, 1160 cur1; nmr (220 MHz) 0.93 (s, 6 H), I. 5-1.9 (m, 8 ), 2.40 (s) and 2.41 (s) (5 H), 7.28 (d, / = 8 Hz, 2 H), 7.38 (s, 1 H), 7.82 (d, / = 8 Hz, 2 H); mp 147.5-150.5°; 10c, ir 3200, 1685, 1160 cm"1; nmr (220 MHz) 0.80 (d, / = 7 Hz, 3 ), 0.92 (d, / = 7 Hz, 3 ), 1.5-2.1 (m, 10 H), 2.32 (d of d, = 17, = 5 Hz, 1 H), 2.42 (s, 3 H), 2.72 (d of d, = 17, = 4 Hz, 1 H), 7.28 (m, 3 ), 7.80 (d, / = 8 Hz, 2 H); mp 137.5-140.5°. having five-, six-, and seven-membered rings and indicated that the yield of cyclopentanone and cyclohexanone from appropriate precursors was significantly higher than yields of cyclobutanones.…”