Condensations by Sodium. XXXVII. The Dimetalation of Benzene, Thiophene, p-t-Butylphenol, Isopropylbenzene and sec-Butylbenzene and the Effect of Alkoxides on the meta:para Ratio for Benzene^1,2

Abstract

Amylsodiurn dimetalates benzene chiefly in the meta position but the ratio of meta to para can be altered by the alkoxide t-Butylphenoxide is attacked which is associated with the reagent. in the 2,6-position.Thiophene is easily dimetalated in the 2,5-positions. Isopropylbenzene and sec-butylbenzene are dimetalated in the 3,5-positions.

Generation of gas‐phase sodiated arenes such as [(Na3(C6H4)+] from benzene dicarboxylate salts

“…The molecular formula of the m / z 145 ion produced when a second CO 2 is eliminated from meta and para isomers is Na 3 C 6 H 4 + , which in fact represents the sodium adduct of phenelenedisodium, an ionic species, which has not been reported previously. Although, aryl derivatives of the alkali metals are known as useful strong bases and potent nucleophiles,22 only on one rare occasion has phenelenedisodium been mentioned in the literature 23. On the other hand, 1,4‐ and 1,3‐dimetalations have been accomplished with ‘spiny’ arenes such as tert ‐butylbenzene 24.…”

Halogen–sodium exchange enables efficient access to organosodium compounds

“…Despite the synthetic promise of such species, the potential of multimetalation remains underutilized, even in organolithium chemistry 3,16,17,27,28 . Double sodiation via deprotonation has been reported 3,14,16,17,[29][30][31][32][33][34][35][36][37][38][39][40][41] , but efficient triple or quadruple sodiation has not been known to date. Our halogen-sodium exchange method enabled the regioselective access to tri-and tetrasodiated compounds (Fig.…”

The 2×3 Toolbox of Organometallic Methods for Regiochemically Exhaustive Functionalization

“…Dimetalated compounds such as phenylenedisodium ( 6 ; as a mixture of meta and para isomers),16, 17 furan‐2,5‐diyldisodium ( 7 a ),18 furan‐2,5‐diyldilithium ( 7 b ),19 thiophene‐2,5‐disodium ( 8 a ),20 thiophene‐2,5‐diyldilithium ( 8 b ),19 and dibenzofuran‐4,6‐diyldisodium ( 9 )21, 22 have been known for a long while (Scheme ). Their synthetic value is quite limited as they can only lead to symmetrically substituted derivatives.…”