INFLUENCE OF STRUCTURE OF QUATERNARY AMMONIUM IONS ON ORTHO SUBSTITUTION REARRANGEMENT VERSUS 1,2-SHIFT WITH SODIUM AMIDE IN LIQUID AMMONIA. INFLUENCE OF TEMPERATURE.¹

The [2,3] sigmatropic rearrangement of N-benzyl-O-allylhydroxylamines

“…ν max (film)/cm Ϫ1 2983 (s), 1879 (w); δ H (400 MHz, CDCl 3 ) 1.41 (3H, d, J 6.4, CH 3 ), 4.80 (1H, app quintet t, J 6. 4…”

“…Of the many rearrangement processes that exist, 1 [2,3] sigmatropic rearrangements have received considerable attention as a method for carbon-carbon and carbonheteroatom bond formation. 2 A variety of substrates have been shown to undergo this transformation, 3 including the Sommelet-Hauser rearrangement of quaternary ammonium salts, 4 the Meisenheimer rearrangement of tertiary amine oxides, 5 the Mislow rearrangement of allylic sulfoxides 6 and the related Wittig and aza-Wittig rearrangements of allylic ethers 7 and amines 8 (Fig. 1).…”

The reaction of chlorosulfonyl isocyanates with allenes and olefins

“…The ether moiety was dried (Na^SOO and evaporated to dryness under a N2 stream. The residue was extracted or dissolved in boiling solvent; the solution was decolorized (charcoal) and cooled to -20°to give the Nchlorosulf onyl-/3-lactam product (8). Concentration of the filtrate occasionally gave additional amounts of product.…”

“…Benzenethiol-Pyridine Reduction of N-Chlorosulfonyl-/3-Lactams ( 8) to /3-Lactams 9.-The general procedure used was as follows. A solution of pyridine (20% mol excess) in acetone (15 ml/0.1 mol) was added dropwise (30 min) to a stirred solution of 8 and benzenethiol (2 equiv) in acetone (25 ml/0.1 mol), maintained at -30°. After stirring for an additional 30 min, an amount of water, equal to the volume of solvent acetone, was added slowly with stirring.…”

“…Recently we reported that the stepwise 1,2-dipolar cycloaddition of chlorosulfonyl isocyante (CSI) to alienes [2,4-dimethyl-2,3-pentadiene (6a), 3-methyl-1,2butadiene (6d), pentamethyleneallene (6e) and 1,2-cyclononadiene (6h) ] proceeded via path a to produce initially, in the transition state, an allyl-type stabilized carbonium ion (7) leading ultimately to /3-lactams (8,9) and/or from the aqueous extract, 2-carboxamido-l,3- :oc-c=c: 10 butadienes (10). 6 The reaction between CSI and 6d produced a third product (11) which seemed to be an adduct of 2 equiv of CSI with one of 6d.5 In this paper, we (i) report on CSI addition to alienes 2-methyl-2,3pentadiene (6b), 2,3-pentadiene (6c), 1,3-diphenylpropadiene (6f), and phenylpropadiene (6g); (ii) provide experimental details of the reaction between CSI and 6a-h, with proof of structure of both /3-lactam and diene amide products; (iii) identify 11 by degradation and independent synthesis; (iv) provide experimental evidence for the stereospecific cycloaddition of CSI to cis-and ¿rcms-/3-methylstyrene (cis and trans 16g),6 and…”