1593 CV1.--Thiocarbimides derived f?.orn Complex Ehlt y Acids, By AuGusrrus EDWARD DIXON, M.D. OUR acquaintance with the fatty acidic thiocarbimides is at present limited to those derived from acids relatively poor in carbon, the highest member of this class hitherto obtained being a raleryl com- pound, CaH9*CO*NCS (Dixon, Trans., 1895, 67, 1040). The lead tbiocyanete process already described for preparing these and allied substances is apparently generic ; it seemed, therefore, of interest to endeavour t o apply it to some of the higher terms of the fatty acid series, and experiments were accordingly carried out in this direc- tion. The results obtained form the subject of the present commu- nication. The process above referred to consists in heating, in a reflux apparatus, the corresponding acid chloride and dry lead thiocyanate, with anhydrous benzene, to the boiling point of the mixture; occa- sionally toluene is preferable, and sometimes even cumene, on account of the higher temperature thereby attainable ; the presence of a solvent is generally essential, for, in its absence, the acid chlor- ide often fails to completely moisten the thiocyanate ; moreover, in some cases, violent action occurs, accompanicd by charring of the materials, if they be heated together without a diluent.Using charges of 20 to 30 grams of chloride, and 50 to 60 C.C. of benzene, with 1& times the theoretical quantity of finely divided lead salt (preferably mixed with about its own weight of dry sand), and keeping the contents of the flask in constant motion, 10 to 15 minutes’ heating, as a rule, is sufficient ; interaction is complete when, after allowing the solid products to completely subside, the clear super- natant liquid no longer affords a green flame coloration, when used to moisten a fragment of copper oxide.Occasionally it prores difficult to obtain a solution free from chlorine; if this end is not attained within 30 minutes, it is generally best to filter a t once through dry paper, by aid of the pump, mix the filtrate (including washings) with a little fresh thiocpanate, and boil up again. As soon as the inter- action is a t an end, the mixture is filtered, well washed with dry benzene, and the filtrate diluted further with the same solvent, so that each litre contains 1 gram-molecule of product; if pure materials are employed and moisture carefully excluded, the yield of dissolved thiocarbiniide is, in most cases, practically quantitative.If possible, the solut,ions should be used without delay; they are apt to decompose on keeping f o r a few days, or it may be, hours, with1594 DIXON : THIOCARBIMIDES DERIVED FROM formation of brownish, insoluble amorphous solids-polymeric forms, very likely, of the thiocarbimides. Unfortunately, no really satisfactory method has yet been found of isolating the dissolved products ; steam distillation is out of the question, as they are all readily attacked by water ; some of them do not distil unchanged under diminished pressure, and even if they do, there is generally heavy loss, owing to the substance being freely carried over with the vapour of the solvent.I. PALMITYLTHIOCARBIMIDE, C15H31*CO*NCS, AND ITS DERIVATIVES. Pure palmitic acid, melting a t 61°, was treated with phosphorus pentachloride, as prescribed by Krafft and Burger (Rer., 1884, 17, 1379) ; the organic chloride, on further treatment with lead thio- cyanate, afforded a yellowish solution of the corresponding thiocarb- imide, the yield of the latter being nearly quantitative, When shaken up with cold water, the solution gave, on the addi- tion of ferric chloride, a distinct red coloration ; if previously boiled with water, the tliiocyanic reaction so obtainable was greatly intensified. C15H3,*CO*NCS + H,O = C15H31*COOH + HSCN. But the dissolved substance is, nevertheless, a thiocarbimide, or, at least, can act as such, for the solution, when mixed with alkaline lead tartrate, is copiously desulphurised on boiling ; ammoniacal nitrate of silver, when added to the alcoholic mixture, affords a curdy white precipitate, which readily blackens on warming ; and, more- over, on treatment with organic bases, union occurs directly, with evolution of heat and production of the corresponding substituted thioureas.Unless, therefore, this compound and its congeners are to be regarded as tautomeric, in the sense of being capable o f acting either as thiocyanate or thiocarbimide, according to the conditions under which they are placed, there seems to be only one way of satisfactorily accounting for the production of thiocyaaic acid, namely, that hydrogen thiocarbimide is initially formed, together with an acid, R*CO*NCS + HZO = R*CO*OH + H*N:C:S, but thereupon undergoes, more or less rapidly, metameric rearrange- ment into the more stable configuration, H*S*CiN. The suggestion here made has already been mentioned in a former paper (Dixon and Doran, Trans., 1895, 67, 5 i 5 ) ; I hope later on ti? investigate the phenomena more fully, particularly with a view to obtain, if possible, the hypothetical intermediate product, H-NCS.In preparing the addition compounds described below, the freshCOMPLEX FATTY ACIDS. 1595 benzene solution was employed ; when cold, it is practically devoid of odour, save that of benzene, but i f heated, ft slight acid thiocarb- imidic smell becomes perceptible ; on exposure to ordinary moist air, it slowly decomposes, owing to hydration, crystals of palmitic acid being deposited.Isolation of the Thiocarbi?wide.-In order to completely expel the solvent, a benzene solution, obtained from 25.6 grams of palmitic acid, was heated to 150' in an oil bath at 12 mm. pressure; on cool- ing, and ullowing i t to remain, the residue solidified to a dark brown, warty-looking mass. On attempting to distil this, a few grams of a clear, pale yellowish liquid of slightly pungent odour were collected, boiling between 200' and 205' under a, pressure of 10 mm. Much decomposition now occurred, gas being evolved, and the pressure riving to about 100 mm. ; ths residue became dark and treacly in consistence, but no more liquid came over. Continuing the heating, the pressure gradually diminished to almost 9 mm., bat still nothing distilled over, and frothing now became so troublesome that the pro- cess had to be stopped.After keeping a few hours, the distillate had darkened somewhat, and presently changed to a brownish solid, melting at the temperature of the hand. It gave reactions similar to those of the benzene solu- tion, and when pressed between folds of bibulous paper, formed a softish mass, which was dried over sulphuric acid and analysed. 0.2029 gare 0.1554 BaSOa. 0.2248 ,, 9.1 C.C. moist nitrogen at 11' and 764 mm. N = 4.85. S = 10.52. ClaHslCO*NCS requires S = 10.78; N = 4-72? per cent. ab-PuEmitylphenyZthiocu~~a~ide, C15H31*CO*NHCS*NH*C6H5, Molecular proportions of aniline, dissolved in benzene, and the thiocarbimide were mixed; heat was at once evolved, the mixture becoming slightly turbid, and, on cooling, the whole gradually solidi- fied.By several recrystallisations from absolute alcohol, very fine, hair-like, interlacing needles were obtained, having a somewhat greasy feel and waxy appearance, and melting at 62-63" (uucorr.). A sulphur determination afforded the following result. 0.2512 gave 0.1476 BaS04. S = 8.08. C,H,,N2S0 requires S = 8-18 per cent. When heated with water, the powder melts, forming a colonrless oil, specifically lighter than the water ; it is quite insoluble in the latter, even at the boiling point, and, on cooling, again solidifies to a crystalline cake ; it dissolves easily in hot alcohol aiid light petro- leum, much more sparing in cold, and freely in ether, chloroform, or benzene.The alcoholic solution gives no colour reaction with ferric1596 DIXON : THIOCARBIMIDES DERIVED FROM chloride; it is desulphurised at once in the cold by ammoniacal nitrate of silver, or by alkaline lead t a trate on boiling. Action of Silver Nitrate.-To a hot alcoholic solution of the above thiocarbamide, a little more than the calculated quantity of silver nitrate, in weak spirit, was added ; silver sulphide was precipitated instantly, and after a few minutes' boiling, the mixture was filtered ; as it cooled, the filtrate deposited palmitylphenylurea, in microscopic needles, melting, after recrystallisation from alcohol, at 90-91' (uncorr.), apparently without decomposition. 0.2228 gave 14 C.C. moist nitrogen at 18' and 777 mm. N = 7-42.C2,H,,N2O, requires N = 7.50 per cent.. The urea is insoluble in water, but when heated with it melts to a colourless, floating oil, which solidifies again on cooling ; it is freely soluble in chloroform, carbon bisulphide, hot alcohol, and hot light petroleum, sparingly in the oold ; very freely in hot, and moderately in cold, benzene, F ab-Palmitylorthotolylfhiocarbamide, C16H31*C O*NH*CS*NH*C6H4*CH3. Heat was evolved on mixing the thiocarbimide with orthotoluidine in benzene solution ; on cooling, tbe mixture remained clear, but pre- sently solidified ; the product, when drained, pressed, and recrystal- lised from boiling absolute alcohol, formed a felted mass of very fine, white needles, melting at 65.5-66.5O (uncorr.). The yield of recrystallised material was 72 per cent.of the theoretical. 0.265 gave 0.1548 BaS04. S = 8.03. C,~H&N,SO requires S = 7.93 per cent. It is insoluble in water, with which, on heating, it behaves like the corresponding phenyl derivative (to aroid repetition, it may here be stated that all the compounds described in the present communi- cation resemble one another in this respect), freely soluble in boiling alcohol, rather sparingly in cold, easily in benzene, ether, and chloro- form. Ferric chioride, added to the solution in dilute alcohol, produces no colour change; silver sulphide is precipitated in the cold on treatment with ammoniacal silver nitrate; the sulphur is also readily withdrawn by boiling with alkaline lead tartrate. Unlike its lower homologues, i t does not appear to give up the contained acid radicle when warmed with dilute aqueous potash.DesuZphurisation.-By treating a boiling dilute alcoholic solution of the thiocarbamide with silver nitrate, as described for the corre- sponding phenyl compound, ab-palmitylorthotolylzcrea was obtained in woolly mawes of very slender, flexible needles ; when recrystallised from spirit, they melted at 98" (uncorr.) without undergoing decom-COMPLEX FATTY AClDS. I597 position, forming a clear brown liquid, and afforded the following result on analysis. 0.2 gave 12.4 C.C. moist nitrogen at 18" and '775 mm. C,,H40N20z requires N = 7-23 per cent. The compound is insoluble i n water, freely soluble in hot alcohol, but only sparingly in cold ; it dissolves easily in chloroform, from which it is precipitated on the addition of light petroleum.N = 7.30. ab-PaZrnity~aratoZyZthiocarbamide, C15H31*CO*NH*CIS*NH*C6H4*CH3. The constituents, dissolved in benzene, united at once wit,h evolu- tion of heat, and, on cooling, the whole solidified to a rather greasy- looking crystalline mass ; by concentrating the mother liquor expressed from this, another less pure crop was obtained, the sum of the two weights amounting to a practically quantitative yield. On recrystallisation from boiling absolute alcohol, beautiful tufts of very delicate, white needles were deposited, melting without decom- position a t 75-76' (uncorr.). 0.2052 gave 0.12 BaS04. In relation to solvents, ferric chloride, silver and lead salts, thi compound resembles, in the main, its ortho-analogue.Desul23hurisutiorz.-The boiling, dilute, alcoholic solution, when treated with silver nitrate, afforded a good yield of the corresponding ab-pairnity Zparatolylurea ; the latter separated in very fiue, flexible needles, melting at 89--90' (uncorr.), without decomposition, and having properties similar to Chose of its isomer already described. On analysis the following figures were obtained. S = 8.04. CzrH40NzS0 requires S = 7.93 per cent. 0.2 gave 12.5 C.C. moist nitrogen at 20' and 775 mm. Cz4H40N202 requires N = 7.23 per cent. N = '7.29. n-PaZm.it y Z-v-methylphenylthiourea, C15H31*CO*N:C (SH) *N(CH3)*C6H,. Obtained, with evolution of hcat, from palmitylthiocarbimide and alcoholic methylaniline ; on slightly concentrating the brownish solution, and allowing it to cool, it solidified ; the product, drained and pressed, as usual, on the pump, was dissolved in boiling absolute alcohol, treated with animal charcoal, and thus obtained in Yery slender, white needles, melting a t 59-60" (uncorr.).The yield of purified substance was nearly 63 per cent. of the theoretical. The formula was checked by analysis. 0.2256 gave 0,1314 BaS04. S = 8.00. Cz4BroNzS0 requires S = 7.93 per cent.1598 DIXON : TBIOCARBIMIDES DERIVED FROJI Palmitylmethylphenylthioureao is insoluble in water, very freely soluble in chloroform, benzene, and hot alcohol, moderateIy in cold. Its alcoholic solution is not affected by boiling wit,h alkaline lead tartrate, and, if treated with ammoniacal nitrate of silver, affords a white precipitate, which darkens only slightly on boiling.If, how- ever, the hot solution be mixed with caustic alkali, and silver nitrate then added, the brownish precipitate of silver oxide at first pro- duced rapidly blackens, owing to the formation of silver sulphide. n-Palmity I- v-phemyl benz y 1 tkiourea, C15H31.CO*N:C (S H)*N( CGH5) *CHP*C6H5. Benzg laniline and the thiocarbimide, in alcohol and benzene res- pectively, interacted spontaneously with evolution of heat, and a clear, brownish liquid was formed, which presently solidified ; the amount of yellowish residue, after draining and pressing, was approximately quantitative. By dissolving in hot alcohol, and adding sufficient water to cause incipient precipitation, the solution, as it cooled, depo- sited the thiourea in very slender needles, melting ac 62-63" (uncorr.).A portion was analysed. 0.2208 gave 0.105 BaS04. S = 6.53. C,,,H,,N,SO requires S = 6.65 per oent. The compound is insoluble in water, easily soluble i n hot alcohol, and moderately in cold ; it is not affected by treatment with alkaline lead tartrate, and, in alcoholic solution, yields a white precipitate, with ammoniacal nitrate of silver, which is barely darkened, even on boiling the mixture. Wsubstitu ted thionreas not uncommonly prove difficult to attack by neutral or ammoniacal silver salts, and occasionally withhold their sulphur altogether ; it is generally possible, nevertheless, t o desul- phurise such compounds by modifying the conditioas, its described in the following experiment. a- PaZinity Z- b-pheny lbenzylurea, C ,,H,,*CO.NH*C O*N (C,H,) .CH,-CsH,. The corresponding thiourea (1 mol.), dissolved in hot absolute alcohol, was mixed with normal caustic alkali (2 mols.), and to the clear mixture, silver nitrate (2 mol.), dissolved in hot, dilute spirit, was added.A brown precipitate of silver oxide formed at once, but after a few seconds, began to darken, and rapidly changed to full black. 'The mixture was boiled for some minutes, a small quantity of strong ammonia added, and the silver sulphide removed with the aid of the pump ; a clear, colourless solution was thus obtained, which was treated with water to incipient precipitation; on cooling, a, white solid separated, which on recrystallisation from boiling spirit,COJIPLEX FATTY ACIDS. 1599 separated in beautiful tufts of pearly needles, becoiiiing moist a t 67", and melting a t 6s-69' (uncorr.).A nitrogen determination gave figures agreeing with those required for the urea. 0.2554 gave 14 C.C. moist nitrogen t i t 17'3' and 748 mm. N = 6.24. C,,H4,N,O2 requires N = 6.05 per cent. This treatment with hot alkali and silver nitrate is more effica- cious in desulphurisiiig thiourea derivatives than a n j other wet method that I am acquainted with ; I have not yet had an opportunity to try it upon a tetra-substitution derivative, but every tri-substituted thiourea. so far examiiied-and a considerable number were tested- yields up its snlphur with ease. Moreover, certain other sulphur- etted compounds, f o r example, the perithiazoline derivatives lately described (Trans., 1896,69, 17 ; 851), and Volhard's '' thiocarbimido- acetic acid " (dioxytliiazole), substances whose sulphur is included in a closed chain, and which are, in consequence, refractory under the ordinary treatment with nmmoniacal silver, or alkaline lead, salts, yield more or less completely to the attack by hot, alkaline silver oxide, It seemed probable that this p~ocess might be applied to trisub- stituted thioureas other than those containing acidic groups ; but, judging from experiments made with n-benzyl-v-methylphenyl-, n-ethyl-v-phenylbcnzyl-, a d tribenzylthioureas, the interaction does not r u n sufficiently smoothly to afford the basis of a satisfactory general method for preparing tri-substituted ureas.11. S TEARY LTH IOCAR BI 31 ID E , C H,.C 0 *NC S , AND ITS D EKIVATIVE s . Stearyl chloride, prepared from pure stearic acid by Krafft. arid Biirger's method (Eoc. cit.), was digested, as already described, with dry lead thiocyanate, shaking constantly. I n about 20 minutes, the benzene solution was free from chlorine; i t was filteied from the insoluble lead salts, the latter well washed, and the filtrate diluted as in the case OE the palmitjl homologue. The clear, golden-yellow solution, when hot, possessed the usual acid thiocarbimidic smell, though only in a slight degree; when cold, it was nearly devoid of odour, excepting that of the solvent. When shaken up with water and treated with ferric chloride, the mixture reacted dis- tinctly for thiocyanic acid, but the full red colorakion was, as usual, developed only after heating.Care was taken, during the preparation, to avoid, as far as practicable, access of moisture, but nevertheless, a certain amount of hydration occurred, and the solu- tions in the course of 24 hours, deposited small quantities of a white crystalline solid, free from sulphur, melting a t 68-69", and consist- ing of stearic acid. The presence of dissolved thiocarbimide was1600 DIXON : THIOCARBIMIDES DERIVED FROM recognised, as before, by its re.ady desulphurisstion under the in- fluence of alkaline lead and silver salts. It is worth mentioning that the course of the former interaction appears to depend largely on the way in which it is carried out ; if, for example, the soiution be mixed with dilute caustic alkali, and the mixture boiled for a few minutes, the product, on .further treatment with alkaline lead solution, will be desulphurised only feebly, whilst another portion, similarly boiled and acidified with dilute hydrochloric acid, gives, on the addition of ferric chloride, an intense thiocyanic reaction.If, however, the sub- stance be directly mixed with the lead solution, and forthwith heated, desulphurisation occurs freely, whilst another portion, mixed with cold alkali, then acidified as before, and treated with ferric chloride, gives only a faint, reaction for tliiocyanic acid. Palmitylt.hiocarb- imide, when similarly treated gave substantially the same resulta ; in this case, however, the alternative behaviour, as thiocyanate, or thio- carbimide, was less sharply marked than with the stearyl homologue.ab- St ear y ~ r t h o tol y Z thiocar banzide, C H,* C 0 *NH C S *NH* CsHd C H,. This was obtained, with evolution of heat, from the thiocarbimide and orthotoluidine, the latter dissolved in absolute alcohol. On cooling, the mixture became solid, owing to the separation of very fine needles, the yield of which amounted t o 93 per cent. of the theoretical ; after being recrystallised from absolute alcohol, they melted at 67-68" (uncorr.), without decomposition, and afforded the following results on analysis. 0.2579 gave 0.1401 BaS04. S = 7.4'7. C26H44N2S0 require8 s = 7-41 per cent. Stearylorthotolylthiocarbamide is insoluble in water, very freely soluble in boiling alcohol, sparingly in cold, freely in chloroform, ether, benzene, and warm light petroleum. I t s alcoholic solution gives no colour with ferric chloride, b u t is blackened at once, on the addition of ammoniacal silver nitrate; t4he substance is also readily desulphurised by boiling with alkaline solution of lead. Steal-ylorthoto1ylurea.-By desulphurisation with silver nitrate, a practically quantitative yield of the above symmetrical urea was obtained ; the crude product had a slightly brownish colour, which it still retained after recrystallisation from spirit ; it melted a t 9 6 9 3 ' (uncorr.).0.2448 gave 14.8 C.C. moist nitrogen a t 19' and 762 mm. N = 6.96. C,sH44N202 requires N = 6.75 per cent. It. is easily soluble in hot alcohol, sparingly in cold, insoluble in water.COMPLEX FATTY ACIDS. 1601 ab- Stear!/ Zme t aay Zy Zthiocarbamid e, C ,,Ha5*C O*NH* C S.NH*C,H, (C H,) 2 .Prepared under the same conditions as the preceding thiocarb- amide; similar phenomena were observed, and the weight of solid product amounted to 92 per cent. of that theoretically obtainable. By recrystallisation f porn absolute alcohol, and treatment with animal charcual, a dark purplish coloration was easily removed, and the solution, as it cooled, deposited fine, lustrous, white needles, becoming moist a t 70", and melting at 71-72" (uncorr.). A sulphur determination gave the following result. 0.2592 gave 0.1385 BaS04. S = 7.34. C21H16N2S0 requires S = 7.18 per cent. The compound is insoluble in water, freely soluble in chloroform, benzene, hot alcohol and ether, moderately in cold, and easily in boil- ing light petroleum, b u t rather sparingly in cold ; it crystallises very well from the last named solvent. DesuZlphurisation.-This was carried out as usual, and a clear, dark red solution obtained, which, on cooling, deposited nearly 77 per cent.of the theoretical yield of ab-stearlllmetaxylyluren, in microscopic needles, melting, without decomposition, a t 92-93" (uncorr.). 0.205 gave 11.6 C.C. moist nitrogeu at 19" and 773 mm. N = 6.62. C2,H,,N,O, requires N = 6*,52 per cent. ab- Steary Z- 2- nap7~t 7~9 It hioca~bamide, C HS5* C 0 *NH*C S*NH*CloH,. Obtained as beEore, using a-naphthylamine ; the product, already practically pure, when recrystallised from absolute alcohol, formed microscopic, white needles melting at 80-81" (nncorr.). 0.2578 gave 0.1266 BaS04.C2gH44N2S0 requires S = 6.84 per cent. The compound is insoluble in water, moderately soluble in hot, and sparingly in cold, alcohol ; with other solvents, and with silver o r lead salts, ii; behaves like tbe metaxylyl analogue. DeszcZphurisatioi~.-A greyish solid was obtained, melting at 114- 115" (uncorr.), and this melting point was not raised by recrystallisa- tioa from alcohol. The very fine needles are insoluble in water, rather sparingly soluble in boiling alcohol, almost insoluble in cold, and consist, as shown by the result of analysis, of the expected stearyl- a-naphth ylu~ea. 0.2046 gave 11-2 C.C. moist nitrogen at 20' and 773 mm. N = 6.40, S = 6.75. C'29H44N202 requires N = 6.21 per cent.DIXON : THIOCARBIMIDES DERIVED FROM n- Steary 1- v-pheizy Ebenzy It hiourea, C17H3s*CO*N:C (SH)*N (C+jHj)* CH,*C,Hj.Stearglthiocarbimide and alcoholic beuzylaniline were mixed ; heat was at once evolved, and a clear, yellowish solution obtained, which, after standing for less than a day, solidified; the yield was very sntisfactory-over 95 per cent. of the theoretical. By recrystallisa- tion from boiling absolute alcohol, extremely fine needles were obtained, free from colour, and melting at 66-66-5' (uncorr.) to it clear, yellow liquid. The composition wits checked by a sulphur determination. 0.2581 gave 0.119 BaS04. S = 6.33. CZHaN2SO requires S = 6.30 per cent. The compound is insoluble in water, freely soluble in boiling alcohol, rather sparingly in cold. Its hot alcoholic solution, on the addition of ammoniacal nitrate of silver, gives a white precipitate, which darkens very slightly on boiling ; it is not perceptibly desul- phurised by heating with alkaline lead tartrate.a- Stearyl-b-pheny Zbenzy EzLrea, C17Hs5*COgNH*C 0.N ( c6&)*C H2*C6Hj. Desulphurisation was carried out by means of caustic alkali and silver nitrate, as already described under the corresponding palmityl compound ; the product, d ter recgstallisation from spirit and further treitment with animal charcoal, was obtained in pure white needles, becoming highly electrical on friction, snd melting at 74-75' (.uncorr.) to a slightly turbid liquid. N = 5.84. 0.2152 gave'll C.C. moist nitrogen a t 19' and 756 mm. C,,H~,N,O, requires N = 5.70 per cent. Iu relation to scilvents, it resembles the thiourea.IU addition to the experiments above mentioned, stearylthiocarb- imide was brought into contact with (1) alcoholic ammonia, (2) piperidine, (3) phenylhydrazine, and (4) benzglamine. With the first, as usual, much decomposition occurred, though only the calcu- lated quantity of ammonia was used, the chief products being thio- cyanic acid and stearamide ; (2) and (3) gave poor yields, and the products could not be obtained in a pure condition ; (4) gave a poor yield of a solid, which, after two recrystallisations from alcohol, occurred in brilliant, pearly plates, becoming slightly moist at 91°, and melting at 96-95' ; it contained no sulphur, and, when burnt for carbon an6 hydrogen, gave figures agreeing nemly wit,h those required for stearylbenzidide, C,,H,,C0.NH.CH,.C6Hj.Two att,emptsCOMPLEX FATTY ACIDS. 1603 to obtain pure stearylphenylthiocarbamide were also unsuccessful, owing, apparently, to contamination of the product with stearic acid. ADDENDUM .-Bewoy 1 thiocarbimide and Die thy la mine. Miquel has placed on record (Ann. Chirn. Phys., 1877, [ 5 ] , 11, 316) the failure of repeated attempts to combine oxygsnated tbiocarb- imides with secondary and tertiary amines ; as an instance, he men- tions that benzoylthiocarbimide, even when heated at 200° with diphenylamine or diethylamine, remains unaltered ; but no further details are given. The selection of diphenylamine for experiment was unfortunate, thie compound being exceptionally difficult to unite with the thio- carbimides ; in fact, the only product of such combination, so far as I know, is a triphenylthiourea, obtained in very small quantity by Gebhardt (Bei-., 1884, 17, 2092) on heating phenylthiocarhimide for several days at 280" with the secondary base.In a, similar experi- ment, made several years ago by myself, using ethylthiocarbimide, and heating under pressure for two hours at 160°, slight decomposi- tion occurred, with formation of sticky bye-products, but no additive compound was obtained. But as regards secondary bases, which are non-, or only partially, benzenoyd in character, union with acidic thiocarbimides takes place, as a rule, quite as rendilyas where primaryare employed; the above- mentioned failure in the case of diet.hylamine was, consequently, rather puzzling ; and it seemed, therefore, desirable to make a,nothei.attempt to ascertain whether combination between these two sub- stances cannot be brought about. Instead of employing the somewhat laborious method described by Miquel for preparing the necessary benzoylthiocarbimide, a sdution of it was made from benzoic chloride (7 grams) and lead thiocyanate by boiling them together in dry benzene, using a reflux condenser ; in about 10 minutes the action was complete, and, on filtering off the insoluble lead compounds, a clear, brown liquid was obtained, to which a trifle over the calculated quantity of diethylamine, in abso- lute alcohol, was added. Marked evolution of heat at once occurred, which was checked by external cooling with water, arid the resultant clear solution, on concentration, deposited yellowish crystals amount- ing to about 90 per cent. of the quantity theoretically obtainable from the weight of materials employed. By washing with benzene, the colour was removed ; the residue, when recrystallised from boiling alcohol, formed long, pure white, brilliant prisms melting at 100-lO1° (corr.), and giving the following result on analysis. 0,2056 gave 0.206 BaS04. S = 13.77. C~HB*CO*N:C(S~)*N(CzH5)2 requires S = 13-57 per cent.1604 CROSS, REVAN, ASD SMITH: Benzoyldiethylthioui*en is sparingly soluble in boiling water, practically insoluble in cold ; almost indefinitely soluble in boiling ethylic or methylic alcohol, moderately in the cold, very freely in chloroform and acetone, less so in ether and benzene. It dissolves easily in cold dilute caustic alkali ; but if to this solution a lead salt be added, and the mixture boiled, no desulphurisation occurs. Ammoniacal nitrate of silver prodnces in the alcoholic solution a white precipitate dissolving on heating and appearing again on cool- ing; if a few drops of caustic alkali be added to the clear, heated solution, silver snlphide is at once formed. Ferric chloride, added to the solution in weak spirit, yields a purplish, amorphous precipitate ; this dissolves on the addition of hydrochloric acid, but reappears on cautious treatment with alkali ; if excess of the latter be used, the colour is destroyed and ferric hydroxide is formed. In carrying out the work described in the present communication, I have received much assistance from Mr. R. E. Doran, to whom I wish t o express my thanks. Chemical Deyavtment, Queen's College, Cork.