Carbon Participation in the Solvolysis of Tertiary Norbornyl Derivatives Norbornanes. Part 15. 6-substituted 2-methylnorbornyl 2-exo- and 2-endo-2,4-dinitrophenyl ethers

✍ Scribed by Cyril A. Grob; Adrian Waldner

• Publisher: John Wiley and Sons
• Year: 1983
• Tongue: German
• Weight: 352 KB
• Volume: 66
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19830660813

✦ Synopsis

The solvolysis rates and products of the tertiary 2-methyl-2-exo-and -2-endonorbornyl 2,4-dinitrophenyl ethers 1 and 2, (X = 2,4-(NO,),C,H,O) have been determined. The different sensitivities of the rates of these ethers to the inductive effect of substituents at C(6) indicate that graded bridging of C (2) by C(6) occurs in the ionization of the exo-ethers 1, not, however, in the ionization of the endo-ethers 2. In both cases hydrolysis leads to 2-methyl-2-exo-norbornanols only. Consequently, substitution takes place with retention at C(2) in the exo-series 1 and with inversion at C(2) in the endo-series 2. It is concluded that stereoelectronic and polar effects, rather than steric bulk effects, determine the high exolendo rate ratios of the parent norbornyl derivatives l a and 2a.