Bamford and Stevens. 4735 924. T h e Decomposition of Toluene-p-sulphonylhydrazones by Alkali.

Syntheses are described of 1.3.5-trisubstituted benzenes with the following substituents CH,CI, CH,OEt, CH,OB,, and [CH,],X (X = OH, OAc, OCB,, CI, Br, CN, or C0,H). an improved route to 1,3,5-tris(hydroxymethyl)benzene and alternative routes to the corresponding tri-aldehyde and tris( bromomethyl) derivative. Strathclyde, GlasgowTHE symmetrically t risubst it ut ed benzene derivatives described here were required by Professor M. Gordon

Under the influence of an alkaline reagent, an ether having a mobile proton may undergo rearrangement (a) or fission (b) :The incidence of these reactions has been examined for phenacyl, 9fluorenyl, and a-cyanobenzyl ethers in butanolic sodium butoxide. But-2-enyl, l-methylallyl, and active a-methylbenzyl ethers of fluoren-9-01 showed unexpected behaviour.THE rearrangement of ethers, CHR,-OR' ---f CR,R'-OH, under energetic alkaline conditions has been recorded by Schorigin and investigated extensively by Wittig2 H a ~s e r , ~ and Curtin and their collaborators. This change is often accompanied or superseded by a process of fission according to the more detailed scheme:Cram, Kingsbury, and Langemann have examined this process of fission in some detail.The main driving force for the rearrangement is no doubt the transference of the formal charge from carbon to the more electronegative oxygen atom; rearrangement of tertiary amines, in which 0 in the scheme is replaced by NR", takes place much less readily (following paper) ; rearrangement of quaternary ammonium compounds : CHRz*&R"2R' __f CR2-GR"2R' + CR2R'.NR''2

No abstract

showed that aliphatic diazocompounds do not combine with tertiary amines as they do with phosphines; diphenyldiazomethane when heated with triethylamine undergoes the same decomposition to benzophenone azine as when heated in other solvents. If the first product of decomposition of the diazo-compound is the uncharged diphenylmethylene radical Ph&, it is conceivable that this will co-ordinate, reversibly, with the amine, giving Ph,C-NEt,, although in the end its fate is to combine with unchanged diazo-compound, yielding the azine. A case might then be found in which the dipolar ion would be stable or would undergo irreversible change to a significant product. We failed to effect the combination of diazofluorene with fluorenone methylimine to give the specially stabilised compound (I) ; -+ c but diazofluorene and benzyldimethylamine afforded a considerable amount of 9-benzyl-9dimethylaminofluorene (11). Wittig and Felletschin (Annalen, 1944, 555, 133) obtained the same compound from (111) via the unstable (IV).