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 rit«print«d from Tbi Cin^iir Rkoobd or SaiNOB, October, 1880.] 
 
 Derivatives of Tolidin. 
 
 R. F. RuiTAN, B.A., M.D. 
 
 In 1845 a BuBsian chemist named Zinin,-' by reducing 
 Azobenzol with hydrogen sulphide obtained a substance 
 which, when further treated with sulphuric acid gave rise to 
 a base called Benzidin. The intermediate product of the 
 reduction of azobenzol was subsequently examined by 
 Hofmann-^ and found to be Hydrazobenzol, and the nature 
 of the reaction giving rise to Benzidin was made clear. 
 
 From a homologue of hydrazobenzol, viz. : hydrazotoluol 
 by Hofmann's method, Petriew * prepared the homologue 
 of Benzidin, viz., Tolidin, and studied some of its charac- 
 teristics. The constitution of both Benzidin and Tolidin 
 was afterwards established by Gustav Schultz.' These 
 two bases were shown by him to be double molecules of 
 anilin and toluidin, respectively, connected by their benzol 
 neuclei, and having their amidogen groups in the para 
 position. Their formulae being : — 
 
 f C, H, NH, ( Cb fl, (Cffa) NH, 
 
 Benzidine I Tolidin-^ I 
 
 \t\H,NH, { C, H, (CH,) NH, 
 
 Benzidin has received some attention from chemists and 
 many of its reactions have been investigated. Tolidin, on 
 the other hand, owing to the difficulty with which it was 
 
 ' In a former communication to this journal, they were referred 
 to as probably at the top of Div. 2. (See July, 1889.) 
 " Journal fiir practische Chemie, xxxvi., 03. 
 * Jahmbuicht der Chemie, 1863, 424. 
 <Berichte,vi.,567. ' 
 
 ^ Liebig's Annaleo, 174, 227. Berichle, xvii., 467. 
 
490 
 
 Canadian Record of Science. 
 
 obtained, and its apparent unimportance, has received until 
 lately no attention whatever. These two bases were long 
 regarded merely as chemical curiosities whose chemical 
 relations were of importance only so far as their existence 
 threw light on other reactions, and thus aided general- 
 ization. A few years ago, however, Greiss' announced that 
 benzidin, like anilin, formed a diazo compound on treatment 
 with nitrous acid. From this Gustav Schultz, of Berlin, in 
 18'79, prepared the first of the now important class of dyes 
 called Azo-dyes from Benzidin, but the first economic dye 
 of this class was patented in 1884 and named Congo red. 
 These dyes, now very numerous, owe their importance in the 
 arts to the fact that they dye wood and cotton fibre directly, 
 i.e., without the use of a mordant. 
 
 The success of the Congo red and other dyes of this class 
 lead to the preparation of these rare bases, Benzidin and 
 Tolidin, in available quantity. Through the kindness of 
 Prof. Hofmann I was enabled to obtain from Gustav 
 Schultz, of the Berlin anilin factory, a kilogramme of 
 crude Tolidin, and began the study of its derivatives in 
 Berlin three years ago. Some of these compounds have 
 already been described by me, and formed part of a paper 
 read before the British Association in 1886,* but others have 
 been obtained since. This paper deals chiefly with those 
 derivatives obtained directly from the base Tolidin, and 
 includes only those secondaiy derivatives necesary to 
 illustrate completely a particularly reaction of the base 
 itself. The subject is, however, by no means worked out as 
 in a direction indicated at the end of this paper, it gives 
 promise of interesting results yet to be obtained. 
 
 The crude base obtained from the factory proved to be 
 the ortho-tolidin, and on purification crystallized in glisten- 
 ing scales of a pale violet hue, melting at 128° C — not at 
 112°, as was originally stated by Petriew.^ It turns in- 
 tensely blue when treated with oxidizing agents, gives a 
 
 ' Journal fiir practische Cbemiei 101, 92, 
 '^ Proc. Brit Ass'n., 1886. 
 •' Loc cit 
 
Derivatives of Tolidin. 
 
 491 
 
 blue color with feiTic chloride when conceDtrated, and green 
 when dilute, when boiled this turns red and gives a precipi- 
 tate of ferric hydrate. The sulphate is very insoluble ; the 
 hydro-chlorate is soluble in water and in alcohol ; it forms with 
 Platinum chloride beautiful yellow acicular crystals, usually 
 in rosettes, insoluble in water and dilute alcohol. These 
 decompose on exposure to moist air, but if dried after pre- 
 cipitation by washing with alcohol and ether, they may be 
 further dried at 100° and analysed. The following results 
 confirm the formula : — 
 
 Q H, {CH,) Nil, 
 4 Ha (CH,) NH, 
 Calculated. 
 Platinum =& 31.07 per cent. 
 
 1 
 
 2ffa, Ptcii 
 
 Found. 
 
 I. II. 
 
 30.81. 30.90. 
 
 Cyanide of Tolidin. 
 
 Cyanogen gas, evolved by heating mercuric cyanide, was 
 slowly passed through a cold saturated alcoholic solution of 
 Tolidin, till a distinct precipitate occurred, the solution was 
 tightly corked and allowed to stand for forty-eight hours. 
 
 A voluminous, brown, amorphous precipitate resulted, 
 which, when filtered and washed with alcohol, ether and 
 benzol, was dried and examined. This product w.'is found to 
 be a reddish brown amorphous body, insoluble in water, 
 alcohol, ether or benzol, very slightly soluble in phenol, 
 ligroin and nito benzol. It did not melt at 320°, and bui-ned 
 with difficulty when heated on platinum. It decomposed 
 into tolidin and oxalic acid when heated with acids. 
 
 In making the combustion of this substance it was found 
 necessary to add lead chromate to the copper oxide to ensure 
 complete oxidation, and even then the combustion was very 
 tedious. The following figures established the formula: — 
 
 Cie ^16 -"4 
 
 2 ^ C^H, {CH,) NH, }- CN 
 
 C 
 H 
 
 N 
 
 Theory. 
 
 72.72 
 
 6.06 
 
 21.21 
 
 I. 
 71.96 
 0.11 
 
 Found. 
 II. 
 71.8 
 6.21 
 
 III. 
 
 21.43 
 
492 
 
 Canadian Record of Science. 
 
 The TMo-urea. 
 
 Twenty grammes of Tolidin in alcohol were boiled with 
 an equal weight of carbon bisulphide in a flask with reversed 
 condenser for six hours. The result was the formation of a 
 white crystalline powder, melting at 185° and insoluble in 
 most media, but soluble in strong sulphuric acid, from which 
 it was precipitated on dilution. Hydrogen sulphide was 
 evolved during the reaction. The resulting compound had 
 the formula: C^^H^^ N^ OS, and the reaction which occurred 
 may be reproscnted thus : 
 
 a H^ NH, 
 
 + cs. 
 
 
 The following ai*e the analytical results : — 
 
 Theory, 
 
 C = 70.86 per cent 
 H =»= 5.50 
 N =« 11.02 
 S =-= 12.01 
 
 I. 
 
 71.11 
 
 6.03 
 
 Found. 
 II. 
 
 71.06 
 5.81 
 
 III. 
 
 12.14 
 
 All attempts to convert this into an iso-sulpho-cyanido 
 by the usual methods were ineffectual. 
 
 Diacetyl Tolidin. 
 
 Tolidin, when boiled for a few hours with t-8 times its 
 weight of glacial acetic acid, in a flask with reversed con- 
 denser, readily forms the diacetyl tolidin. The same sub- 
 stance is at once formed in the cold when acetic anhydride 
 is added to a solution of the base. It is a white crystalline 
 l)0wder,^ melting above 320° and insoluble in the usual sol- 
 vents. It is deposited, however, in snow white needles on 
 cooling its solution in boiling nitro benzol ; when thus puri- 
 fied and dried at 130° it yielded the following analytical 
 data : — 
 
 Calculated for C,8 
 
 Thcori). 
 
 H,o N, 
 
 O, 
 
 C 
 H 
 
 N 
 
 
 72.97 
 6.76 
 9.46 
 
 10.81 
 
 I. 
 
 72.62 
 
 6.88 
 
 ...» 
 
 • ••• 
 
 Found. 
 II. 
 72.29 
 6.59 
 
 III. 
 
 9.75 
 
Derivatives of Tolidin. 
 
 493 
 
 Tetra-acetyl Tolidin. 
 
 This is probably the most interesting of all the deriva- 
 tions of Tolidin, inasmuch as it is, with one exception, the 
 only example of a primary base in which both of the hydro- 
 gen atoms in the amidogen group (NH^) have been re- 
 placed by the acetyl radicle. The only other compound of 
 this class is Diacetanilid.* C„ H^ N(G.,H^ 0),. Hofmann 
 prepared this by the action of glacial acetic acid on phenyl 
 mustard oil in a sealed tube at 130° — 140 C. 
 
 C.H, NCS + 2C\H,0, = G,H, N iO,II,0\ + GO, 
 
 From the readiness with which the acetyl radicle united 
 with the tolidin it was supposed that a similar compound 
 might be obtained directly by treating diacetyl tolidin with 
 acetic anhydride. Accordingly diacetyl tolidin was, with 
 6-7 times its weight of acetic anhydride sealed in tubes and 
 submitted to a temperature of 180" C for six houi-s. The 
 tubes were then found to contain in a dark fluid acicular 
 crystals, which were soluble in alcohol, ether, benzol and 
 and acetic acid, but insoluble in water. After purification, 
 the substance was found to crystallize in long, silky, snow 
 white needles, melting at 210° and on analysis gave the 
 following results : — 
 
 Calculated for Cj, H.^ N.^ 0^ 
 
 Theory. 
 
 Fmmd. 
 
 
 I. II. 
 
 C= 69.47 
 
 69.28 
 
 H= 6.32 
 
 6.61 
 
 i\r= 7.37 
 
 7.65 
 
 = 16.84 
 
 • • • ■ • • • I 
 
 When treated with dilute alkalies it at once broke down 
 into diacetyl tolidin and acetic acid. The two acetyl deriva- 
 tions of Tolidin may be thus represented : — 
 
 I fC,H,0 
 
 4 h,-n{ c, h, 
 
 DiAOBiyivTounui. 
 
 CH, 
 
 fC,H, 
 
 
 
 o 
 
 I fc:,H,o 
 
 V,H,-N\C,H, 
 Tbtka-aubtyl ToLiniN. 
 
494 
 
 Canadian Record of Science. 
 
 Binitio-diactylrtolidin. 
 
 Diacetyl tolidin is easily nitrated when added in small 
 quantities to faming nitric acid, and the violence of the 
 reaction moderated by surrounding the flask with ice cold 
 water and maintaining a large excess of nitric acid. The 
 mixture is then poured into a long beaker filled with 
 snow and the precipitated nitro body filtered and washed. 
 It is insoluble in alcohol, water and the usual media, but 
 may be, like diactyl tolidin, purified by precipitation from 
 solution in boiling nitro benzol. This compound, at firet of 
 a brown tint, can be obtained almost white by repeated re- 
 crystallization. It does not melt, and when an attempt was 
 made to purify by sublimation it exploded violently. 
 
 On combustion it yielded the following data : — 
 
 Calculated for C,8 if,8 ^^ Og 
 
 Theory. Found. 
 
 C=- 55.96 55.73 
 
 H=Mz 4.66 482 
 
 iV^=-= 14.51 .... 15.10 
 
 0=- 24.87 
 
 These results are in conformity with the formula : — 
 
 CH, 
 
 \ fH , . 
 
 NO.,—t\ H^—Ni C, H^O 
 
 CH, 
 
 Dinitro-toUdin. 
 When the body above described is saponified by pro- 
 longed boiling with strong caustic potash a red compound 
 results, which from a large volume of boiling dilute alcohol 
 may be obtained in garnet red tabular crystals which melt 
 at 265° and explode on heating to a higher temperature. It 
 is with difficulty dissolved in any ordinary solvent. 
 It yielded on analysis the following results : — 
 Calculated for C^ H^ JV^ O^ 
 Theory. 
 
 C =. 55.63 
 H= 4.66 
 N=18.5i 
 =« 21.16 
 
 Found. 
 I. II. 
 
 55-87 .... 
 4.91 
 .... 18.10 
 
Derivatives of Tolidin. 495 
 
 This points to the following as the probable formula : — 
 
 ck 
 
 It was thought probable that this compound like other 
 nitro derivatives of the aromatic series might be reduced 
 and a tetra-amido derivative thus obtained but this reduc- 
 tion could not be affected. \^ hen dinito tolidin is submitted 
 to the reducing action of nascent hydrogen, evolved either 
 from tin and hydrochloric acid or from sodium amalgam, 
 it breaks down into tolidin, and by no means employed 
 could the nitro groups be reduced to amidogen. 
 
 (Continued.) 
 
 Chbmical Laboratoby, 
 
 McGill Univ., Med. Faculty. 
 
 October, 1889. 
 
 !