Di--tolyl

Prepared by F. C. Whitmore, N. Thurman, and Frances H. Hamilton. Checked by J. B. Conant and F. C. Whidden. 

In a 2-1. round-bottom flask fitted with a reflux condenser and an efficient glass stirrer, are placed 700 cc. of 95 per cent ethyl alcohol, 100 g. of recrystallized p-tolylmercuric chloride (p. 99), and 160 g. of sodium iodide (80 per cent excess). This mixture is boiled with vigorous stirring (Note 2) for fifteen hours the solid does not entirely enter into solution at any time. The mixture is then thoroughly cooled and filtered by suction and the solid washed with water until free of inorganic halide. It is then dried in an air-oven at 40° and recrystallized from 500 cc. of boiling xylene (Note 3). In this way 45-50 g. (78-85 per cent of the theoretical amount) of a product melting at 238° is obtained. 

Stirring decreases the time required for the reaction and increases the yield. Without stirring it is practically impossible to obtain a product which is free from halogen. 

Since the mercury ditolyl has practically the same solubility in xylene as the tolylmercuric iodide and chloride, the latter will be present in the recrystallized product if the reaction has not gone to completion. A trace of unchanged product may readily be detected by the metallic sodium test for inorganic halides. 

Mercury di-p-tolyl has also been prepared by boiling -bromotoluene with sodium amalgam in xylene in the presence of ethyl acetate as a catalyst.1 

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ET-IR spectroscopy was employed to investigate the structures of the 1 1 complexes between Li" and the guanidine-substituted azo compounds pyiidine-2-azo-p-phenyltetramethylguanidine and 4,4 -bis(tetramethylguanidine)azoben-zene. Both Li" complexes exist as dimers in acetonitrile solution.The structural chemistry of potassium N,N -di(tolyl)formamidinate complexes has been investigated in detail. These compounds were prepared by deprotonation of the parent Af,N -di(tolyl)formamidines with potassium hydride (Scheme 13). The resulting adducts with either THE or DME display one-dimensional polymeric solid-state structures that exhibit /r-fj fj -coordinated formamidinates. 

The chief impurity is l,5-di- -tolyl-3-methyl-1,4-pent-azadiene (m.p. 148°). This can be removed by fractional crystallization, but it is easier to sublime the triazene from the reaction mixture. 

Tolylmercuric chloride has been prepared from />-toluene-sulfinic acid and mercuric chloride,1 from /)-toluenesulfochloride and mercury diphenyl at 1200,2 by treating />-tolueneboric acid with mercuric chloride,3 by the direct mercuration of toluene with mercuric acetate,4 from -tolylmercuric nitrate and hydrochloric acid,5 from hydrochloric acid and / -tolylmercuric hydroxide formed by the oxidation of mercury di-/>-tolyl,6 and from mercury di-/>-tolyl by heating with mercuric chloride in alcohol.7... 

Dimethyl-diphenyl-sulfide. See Di(tolyl)-sulfide in this Vol... 

Di(tolyl) -disulfides or Dimethyl-diphenyl-disulfide and Derivatives... 

Di(tolyl) -ethylenediamine. See Bis(methyl-phenyl-amino)-ethane in Vol 2, p B150-R... 

Di(tolyl)-sulfide, (H C.C6H4)2S, mw 214.32. Several isomers are known ... 

Di(tolyl)-trimethylene-diamine. See Bis-(methylphenylamino)-propane in Vol 2, p B151-L... 

Tetranitro, CjjH NgOg, and Hexanitro, CibH10NsO]3, derivs of Di(tolyl)-urea were not found in the literature thru 1966... 

Another ready source of a suitable 2-mercaptobcnzaldehyde derivative (12) stems from the Rieche formylation of di-/>-tolyl disulfide (Scheme 9). 

Di (tolyl)-ethylenedianiine see Bis (methylphenyl-amino)-ethane 2 B150... 

N,N -Di (tolyl)-guanidine and derivs 5 D1516 NjN -di [2 ( )-nitrotolyl] -guanidine 5 D1516... 

Di (tolyl)-hydrazine and derivs 5 D1516—D1517 dinitro-N, N -ditolyl-hy drazine 5 D1516 4,6,4, 6 -tetranitro-di(m-tolyl)-hydrazine 5D1517... 

Di (tolyl)-phthalide and derivs 5 D1517 3,3-bis (3-nitro4-methylphenyl)-phthalide 5D1517... 

Di (tolyl)-propionic acid and derivs 5D1517—D1518... 

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