| Autor: |
Dahlén A; Organic Chemistry, Department of Chemistry, Göteborg University, SE-412 96 Göteborg, Sweden., Hilmersson G, Knettle BW, Flowers RA 2nd |
| Jazyk: |
angličtina |
| Zdroj: |
The Journal of organic chemistry [J Org Chem] 2003 Jun 13; Vol. 68 (12), pp. 4870-5. |
| DOI: |
10.1021/jo034173t |
| Abstrakt: |
Mixtures of SmI(2)/H(2)O/amine have been found to reduce alkyl halides more efficiently than SmI(2)/HMPA/alcohol mixtures at room temperature. Alkyl and aryl iodides were quantitatively reduced in <1 min and alkyl bromides in 10 min, while alkyl and aryl chlorides required more than 5 h for completion. Determination of the reaction order of Et(3)N in the reduction of 1-chlorodecane showed that the reaction order is one. Water was shown not to participate in the rate-determining step of this reduction. There was a significant change of the UV-vis spectrum and color of SmI(2) upon addition of either PMDTA or water, while no effect was observed with the addition of Et(3)N or TMEDA. Although the combination of SmI(2), water, and amines produces a very efficient reducing system, cyclic voltammetric experiments showed that the redox potential is nearly identical with that of SmI(2) alone. These results are consistent with precipitation providing the driving force for reduction. Taken together, the results of these experiments show that the combination of SmI(2)/H(2)O/amine provides a fundamentally novel and useful approach to enhance the reactivity of SmI(2). |
| Databáze: |
MEDLINE |
| Externí odkaz: |
|
