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Hindered Nucleophilic Displacement (SN 2) Reactions of 2exo- and 2endo- Norbornyl Derivatives. Norbornane) Series 4

✍ Scribed by Cyril A. Grob; Erich Lutz

Publisher
John Wiley and Sons
Year
1981
Tongue
German
Weight
440 KB
Volume
64
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

The reactions of 2__exo__‐ and 2__endo__‐norbornyl bromide (1e and 2e, respectively) in 90% ethanol with a large excess of potassium hydroxide, and of 2__exo__‐norbornyl p‐toluenesulfonate (1g) with excess sodium thiophenolate in methyl cellosolve, have been studied. They obey the first order rate law and are zero order with respect to the base‐nucleophile. However, the ratio of 1,2‐ and 1,3‐elimination to exo‐substitution products depends strongly on the base‐nucleophile concentration. Ion pair intermediates are indicated. The extreme inertness of 2‐norbornyl derivatives in displacement reactions is due to severe steric hindrance of rearside nucleophilic attack, a feature they have in common with other bi‐ and tricyclic molecules bearing nucleofugal groups adjacent to one or two bridgehead atoms.

📜 SIMILAR VOLUMES

Carbon Participation in the Solvolysis o
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
✍ Cyril A. Grob; Adrian Waldner 📂 Article 📅 1983 🏛 John Wiley and Sons 🌐 German ⚖ 352 KB 👁 1 views

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 o