Free-Radical Chain-Substitution Reactions of Alkylmercury Halides

Journal of the American Chemical Society

Volumn 105, Issue 5, 1983, Pages 1398-1399

  Russell, Glen A ^a   Tashtoush, Hasan ^a  

^a IOWA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001086740     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00343a069     Document Type: Article

References (14)

1. Supported by Grant CHE-81 1934 3 from the National Science Foundation and a scholarship to H. T. from Yarmouk University, Jordan.
2. Russell, G. A.; Hershberger, J.; Owens, K. J. Am. Chem. Soc. 1979, 101, 1312.
3. Russell, G. A.; Hershberger, J. J. Am. Chem. Soc. 1980, 102, 7603.
4. Russell, G. A.; Hershberger, J.; Owens, K. J. Organomet. Chem. 1982, 225, 43.
5. 2 attack on PhSSPh and has essentially no reactivity toward PhS” (unpublished results with J. Tanko).
6. The thermal reaction of PhSeSePh and PhTeTePh with dialkylmercurials has been reported without mechanistic interpretation: Okamoto, Y.; Yano, T. J. Organomet. Chem. 1971, 29, 99.
7. Based on a unimolecular cyclization rate constant of 1 X 105 s″1 for the A5-hexenyl radical (Griller, D.; Ingold, K. U. Acc. Chem. Res. 1980, 13, 317).
8. Free-radical reactions leading to cyclopropylcarbinyl products have been reported for homoallylcobalt compounds: Ashcroft, M. R.; Bury, A.; Cooksey, C. J.; Davies, A. G.; Gupta, B. D.; Johnson, M. D.; Morris, H. J. Organomet. Chem. 1980, 195, 89.
9. n-Alkylmercury chlorides or (n-Bu)2Hg react with CC13. to give alkyl radicals with little involvement of the elimination reaction observed for certain dialkylmercurials by Nugent and Kochi: Nugent, W. A.; Kochi, J. K. J. Organomet. Chem. 1977, 124, 327.
10. 2 reaction, R. + PhSHgR’ -> PhSR + HgR', has been observed for R = i-Pr, R’ = Ph and for R = R’ = n-Bu. However, PhSSPh is much more reactive than PhSHgBu and undoubtedly more reactive than PhSHgCl in this process.
11. 4 to yield RC1 or RBr apparently involves the reaction sequence 4a-c among other processes: Giese, B. Angew. Chem., Int. Ed. Engl. 1976, 15, 173, 174.
12. Racemization of chiral organomercurials by a free-radical chain quite likely proceeds by reactions 4a, b; for pertinent references see: Jensen, F. R.; Rickborn, B. “Electrophilic Substitution of Organomercurials”; McGraw-Hill: New York, 1968.
13. Electrophilic cleavage of the A5-hexenyl moiety by PhSH is discounted because of the total inhibition of the reaction by (Me3C)2NO. (Table I).
14. 2HgQYPH are discounted because of the cychzation observed in the reactions of δ5 -hexenylmercurials.