ON A NEW BULPHO ACID OF PHENANTHRENE.
203
In the Aame way, I hope to arrive .at the constitution of pyrene, which is C,,H,, only, in this case, I am not certain wliat position the carbon atoms hold, and will, therefore, have t o try all the three bromtolyl bromides. If we combine two molecules of, say, metahromtolyl bromide, and treat the mixture with sodium, we should get a bihydrated pyrene, and this, treated with H,SO,, should yield pure pyrene.
xxIu.-oN
A NEW S U L P H O
ACIDOF
PHENANTHRENE.
BY HENRYMORTON AND WILLIAM E. QEYER.
A monosulpho acid of phenanthrene was first prepared by Graebe,* and subsequently by Rehs. t Graebe heats phenanthrene with itti own weight of oil of vitriol, for some time, on the water-bath. Rehs uses slightly fuming acid, apparently a t ordinary temperatures. Rlerz and Weith 1 have shown that when naphthalene is heated with sulphuric acid, a t looo, tr-naphthalene Rulpho acid is the main product, but if the temperature is raised to 160-l7Oo, the fi modification is almost exclusively formed. W e h a r e found that in the same way, phenanthrene, also, forms two distinct monoxulpho acids. T h a t formed according to Graebe's method, we propose t o call t h e tr-acid, ours the P-naphthalene sulpho acid. To serve as a means of comparison, we first prepared the n-acid. The process is simple, but the yield is small, the greater part of the phenantlirenc remaining unattacked. T o prepare the &acid, three parts of phenanthrene were heated with two parts of sulphuric acid, in a paraffine bath, t o 1 70°, for three hours. Towards the end, the temperature was, for a short time, raised to 190'. Mach vapor of water and sulphurous acid were given off, during the entire time of heating. On cooling, there was obtained a very black, tenacior~s pitch. This, with the exception of a little unaltered phenanthrene, dissolves in water to a very dark greenish-black liqnid. Wlien this liquid is much diluted, heated to boiling, and neutralized with lead carbonate, the black coloring matter is completely carried down with ~
*Ann Chem. u. Pharm., 167, 102. tBer. d. d. chem. Ocsell., IO, 1353.
iBer. d. d. chem. Oesell., 3, 195.
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t h e lead sulphate, and, on filtering bot, we obtain a t oiioe an almo.qt colorless liquid, from which. 011 c*ooliiig,:L iiearly pure lead salt o f the P-acid s e p r a t e s . By loiig cont inuerl digestion with h i l i n g watw, it can be rcciissulvcd :m(1 p i i t i t i c d liy It~c,i.y..talliziitioii. T h e fiiicl! divided salt is suspeiitled i i i wat(,r, ; i i i d t i m t e d with siiIlhiircttt~(1 Iiydrogen. 011evapomting tlie tiltrate fi.oiii t h e load sull~liiile,i v e obtaiii a thick syriip, \vliic*h sooii c~r!atxliizt~.. ' l ' l i ~ ~ yield ii: ~ r i i n l l : we h a v e riot j e t I i : u i t i i i i c t o vary ~)i~~)portioiis, t c n i p m t iiw. : i i i t l t i i i i r of heating, t o ;~scertninthe Iwst coiiditioiis. /i-p hen an t 11re I i e Y 1I 1ph u aci (1car)-s t :d 1i xes i n fi 11e , ur11 i t 1' t I ecd i cs, u'i t 1I R strong, pearly iiistre. I t is gre;isy t o tlic toiic.11, very solnhle i i i water and alcoliol, but ~iot,~lc~liyiie. Ilt. Its s a l t s :ire! I I I I I C ~l t l ~ q>0111I)le than the c.orrespoiic1iiig cr-salts. It i s LL powerfiil acid, displaciiiy, f o r irist:iiice, c l i l o i i n c a , aiitl I,i'evipit.ztiirg its own salt ~ v l i e i i a wlritioii of the wit1 is atldetl t o :I solution of tlir chlorides of potassium, s o dium, aniniotiiiini, lxwiutn, culciuni, ziiiv, ciolqwr, et(.. ol)tiiiiied i n iiidist,inc*tly crysLead salt, : (C14€19SO~~)21'i~ + talline artists, 011 evapoi,atirig t l i c s ~ ~ l i ~ t i c ~After ii. drying 1)eta.wii blotting-pxper, its weight i l l tlir air is ~ ~ o t i s t a ~ i2t ..4 9 4 grins, driccl a t 1 ~ ~ - 1 6 0 "losc. , 0. 1 7:i. C'illeulated for 3 I I g O . 6.96 per cent.
&O,
Founcl. 6.93 per pent.
0.160 grni of the salt, dried a t ItiO', gave 0.193 BaSO,. For1nd.
Calculated for ,lI,SO,),Pb. 28.71 per cent. (
