P-Tolyl-sodium

The formation of an organosodium compound (p-tolyl-sodium) is well illustrated by the interaction of sodium sand or wire with p-chlorotoluene in light petroleum (b.p. 40-60°) at about 25°, for when the reaction mixture is added to excess of solid carbon dioxide pure/ -toluic acid is obtained directly in a yield exceeding 70 per cent. ... 

In the second, a trace of toluene (possibly formed by hydrolysis) is metalated by the p-tolyl-sodium to give benzyl-sodium and toluene. Since the toluene is regenerated in the reaction, a small quantity would be adequate as a sort of catalyst. 

Pure -xylene may be prepared from p tolyl-sodium and methyl iodide or methyl sulphate. 

In closely related studies, the molecular and crystal structures of lithium, sodium and potassium N,N -di(p-tolyl)formamidinate and N,N -di(2,6-dialkyl-phenyl)formamidinate complexes have been elucidated. These showed the anions to be versatile ligands for alkali metals, exhibiting a wide variety of binding modes. ... 

Allyl p-tolyl sulphoxide 535 reacts with sodium methoxide in methanol by initial prototropic isomerization and subsequent addition of methanol to give 536 (equation 333). Protic solvents are photochemically incorporated by the open chain olefinic bond of trans methyl )S-styryl sulphoxide 537 in a Markovnikov regiospecificity (equation 334). Mercaptanes and thiophenols add to vinyl sulphoxides in a similar manner (compare also Reference 604 and Section IV.B.3) to give fi-alkylthio(arylthio)ethyl sulphoxides 538 (equation 335). Addition of deuteriated thio-phenol (PhSD) to optically active p-tolyl vinyl sulphoxide is accompanied by a low asymmetric a-induction not exceeding 10% (equation 336) . Addition of amines to vinyl sulphoxides proceeds in the same way giving )S-aminoethyl sulphoxides in good to quantitative yields depending on the substituents at the vinyl moiety When optically active p-tolyl vinyl sulphoxides are used in this reaction, diastereoisomeric mixtures are always formed and asymmetric induction at the p- and a-carbon atoms is 80 20 (R = H, R = Me) and 1.8 1 (R = Me, R = H), respectively (equation 337) ... 

Oxidation of 158 and 159 with sodium amalgam as well as of 170 and 171 with ferrocenium (Cp2Fe+) leads to dinuclear N2-bridged products 173, converted to iron(m) and cobalt(m) imides 174 under action of adamantyl and p-tolyl azides (Scheme 66) <2003JA10782>. 

The dissociation pressure of trimethylborane over the adduct is 23 Torr at room temperature and trimethylborane is readily pumped off in vacuo. Tri-ethylborane and triphenylborane did not afford adducts with diphenylketimine also, the B-phenyl derivatives could not be prepared. However, the reaction between di(p-tolyl)methyleneimine hydrochloride and sodium tetraphenylboiate... 

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