𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Norbornanes. Part 10. Solvolysis of the Stereoisomeric 6-Cyano-2-norbornyl p-Toluenesulfonates. A Correction

✍ Scribed by Cyril A. Grob; Danielle Herzfeld

Publisher
John Wiley and Sons
Year
1982
Tongue
German
Weight
310 KB
Volume
65
Category
Article
ISSN
0018-019X

No coin nor oath required. For personal study only.

✦ Synopsis

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__endo__‐alcohol 9 (RCN) beside the 2__exo__‐alcohol 10 and the norbornenes 12 and 13. The results confirm that ‐ I substituents at C(6) reduce 1,3‐bridging in the intermediate norbornyl cation and hence its rate of rearrangement. The relatively high rate constants for some 6‐fluoro‐ and 6‐cyano‐2__exo__ norbornyl p‐toluenesulfonates are ascribed to C, C‐hyperconjugation assisted by the conjugative effects of the 6‐fluoro and cyano substituents.

📜 SIMILAR VOLUMES

Carbon Participation in the Solvolysis o
Carbon Participation in the Solvolysis of 6-endo-Substituted 2-exo-Norbornyl Toluenesulfonates. Norbornanes part 6
✍ Cyril A. Grob; Bettina Günther; Reinhard Hanreich 📂 Article 📅 1981 🏛 John Wiley and Sons 🌐 German ⚖ 471 KB 👁 1 views

## 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

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 👁 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