𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Carbon Participation in the Solvolysis of 6-endo-Substituted 2-exo-Norbornyl Toluenesulfonates. Norbornanes part 6

✍ Scribed by Cyril A. Grob; Bettina Günther; Reinhard Hanreich

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

No coin nor oath required. For personal study only.

✦ Synopsis

Abstract

The solvolysis rate constants k for the 6‐endo‐substituted 2‐exo‐norbornyl toluenesulfonates 7 have been determined. Values of log__k__ correlate well with the respective inductive constants of the substitutents except when the latter are nucleophilic and therefore lead to endo‐cyclization, or when they are n‐electron donors and cause concerted fragmentation. In general 6‐endo‐substituted tosylates 7 react somewhat more slowly than their 6‐exo‐epimers.

Identical or different mixtures were obtained from the C(6)‐epimers 7 and 1 depending on whether the substituent was an electron donor or acceptor. It is concluded that donor substituents at C(6) enhance 1,3‐bridging in the intermediate epimeric cations and lead to their rapid and complete equilibration, and that electron acceptors reduce bridging and hence their equilibration rates.

📜 SIMILAR VOLUMES

Carbon Participation in the Solvolysis o
Carbon Participation in the Solvolysis of 6- and 7-Substituted 2-Norbornyl p-Toluenesulfonates. Norbornanes, Part 11
✍ Peter Flury; Cyril A. Grob 📂 Article 📅 1983 🏛 John Wiley and Sons 🌐 German ⚖ 473 KB 👁 1 views

## Abstract The solvolysis rates and products of several 7‐__anti__‐substituted 2‐__endo__‐norbornyl __p__‐toluenesulfonates **11** have been determined and compared with those of the previously reported 6‐__exo__‐substituted 2‐__exo__‐norbornyl __p__‐toluenesulfonates **1.** Although the number of

Polar versus steric effects in the solvo
Polar versus steric effects in the solvolysis of 6endo-substituted 2endo-norbornyl p-toluenesulfonates. Norbornanes, Part 8
✍ Cyril A. Grob; Bettina Günther; Reinhard Hanreich 📂 Article 📅 1982 🏛 John Wiley and Sons 🌐 German ⚖ 337 KB 👁 1 views

## Abstract The solvolysis rates and products of the 6__endo__‐R‐substituted 2__endo__‐norbornyl toluenesulfonates **6a**–**6i** have been determined. The rates of **6a**–**6g** correlate with the inductive constants σ the 6__endo__‐substituents and are not related to the size of the latter. It is

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

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

Norbornanes. Part 10. Solvolysis of the
Norbornanes. Part 10. Solvolysis of the Stereoisomeric 6-Cyano-2-norbornyl p-Toluenesulfonates. A Correction
✍ Cyril A. Grob; Danielle Herzfeld 📂 Article 📅 1982 🏛 John Wiley and Sons 🌐 German ⚖ 310 KB

## Abstract The solvolysis products of the stereoisomeric 6‐cyano‐2‐norbornyl __p__‐toluene sulfonates **1**‐**4** (R  CN) in dioxane/water 7 : 3 have been determined. In contrast to an earlier report the 6__exo__‐cyano‐2__exo__‐norbornyl __p__‐toluenesulfonate (**1**; RCN) yields 30% of the 2__e

Polar effects. Part 12. Inductivity and
Polar effects. Part 12. Inductivity and carbon participation in the solvolysis of 4-substituted 2-adamantyl arenesulfonates
✍ Cyril A. Grob; Gerhard Wittwer; K. Rama Rao 📂 Article 📅 1985 🏛 John Wiley and Sons 🌐 German ⚖ 480 KB 👁 1 views

## Abstract The rate constants (log __k__) for the solvolysis of 4^e^‐substituted 2^e^‐ and 2^a^‐adamantyl __p__‐nitrobenzenesulfonates **14** and **15**, respectively, in 80% EtOH correlate linearly with the respective inductive substituent constants σ. Therefore, relative rates are controlled by