- UNE VOIE ORIGINALE ET SELECTIVE DE FONCTIONNALISATION EN POSITION META DU FLUORO- ET DE L'ETHYLBENZENE
-
An original and regioselective method for the meta functionalisation of fluoro- and ethylbenze is reported.This process involves a 2,5-disilylation of these subtrates using trimethylchlorosilane in the presence of lithium in THF as the solvent.After aromatisation, monodesilylation in position 2- and electrophilic substitution of the trimethylsilyl group in position 5-, meta acetyl-, senecioyl-, benzoyl-, and iodofluorobenzenes and ethylbenzenes as well as the sodium salts of metafluoro or meta ethylbenzenesulfonic acid and 3-aminosulfonylfluorobenzene were obtained in good yields. pair of diastereomeric triamines 15 and 16.A tricyclic diazasystem 19 was formed from the reaction of cyanide with the carbamoylated chloroenamine 18.Monochloroenamine 10a and dichloroenamine 12a showed a significant mutagenic behaviour in the Ames test.
- Bennetau, Bernhard,Krempp, Michele,Dunogues, Jacques,Ratton, Serge
-
p. 8131 - 8142
(2007/10/02)
-
- Carbanion Rearrangements by Intramolecular 1,ω Proton Shifts, III. The Reaction of 2-, 3-, 4-, and 5-Phenylalkyllithium Compounds
-
Upon addition of THF to a solution of 4-phenylbutyllithium (2) in diethyl ether a rapid intramolecular 1,4 proton shift takes place with the formation of 1-phenylbutyllithium (5).Similarly, although somewhat more slowly, 5-phenylpentyllithium (82) rearranges to 1-phenylpentyllithium (83) via 1,5 proton transfer.The corresponding rearrangements by 1,2 or 1,3 hydrogen shifts, however, starting with 2-phenylethyllithium (1) and 3-phenylpropyllithium (54), respectively, were not detected.With 3-phenylpropyllithium (54) a slow intramolecular 1,5 transfer an ortho proton is observed instead, yielding o-propylphenyllithium (100).The corresponding 1,6 shift with 4-phenylbutyllithium (2) was also detected in a minor amount in addition to the 1,4 proton shift already mentioned.There is no indication, however, for a 1,4 transfer of an ortho proton in 2-phenylethyllithium (1).The reaction products in this case can be exclusively explained by intermolecular transmetallation reactions.All ω-phenylalkyllithium compounds under investigation show interesting side and secondary reactions being rather different in deuterated solvents and in deuteriumfree solvents, respectively, due to the isotope effects.The analysis of the products is accomplished by 1H-NMR spectroscopy and, after derivatization, with the help of a GC-MS-combination.Stereoelectronic reasons are made responsible for the failure of the intramolecular 1,2 and 1,3 proton shift in these systems.
- Maercker, Adalbert,Passlack, Michael
-
p. 540 - 577
(2007/10/02)
-