XLV.-ON
THE
ACTION O F HYIWNI~I’KIC A S ~ I Y I ) K IoLs ) E ORGASIC ~OIJIIBEIlT
11.
L,Cl \\.liicli w e i ~u1)taincd whcn hyponitric anhydride was rnatlc t o avt ; I t varioii,. tcinpcratiircs upon benzene, naphtlialcnc and cyinciic. M y ollject i n the presc,iit paper is to prcswt, i n conformity with t h y 1iiviiiiw niatle :it t1i:it time, the resuits of the action of hyponitric aniiydriile upon a variety of other
orgauic bodies. IV.---ACTIOS
U P O X TOLUENE.
I n the latter part of N a y , 250 grnis of toluene were treated with t h e anhydride until tlic product ceased to increase in weight. It was then poured froni the five flat evaporating dishes, in which it had been hyponitrified, into :L flask, and l e f t with only a sheet of filter paper ticd over t,he inouth of the flask, until the end of the follolving September. l i y this time all smell of the excess of dissolved an1iytlr;de had diffused off, and a red oil remained, with numerous large whitrl. crystals at the sides and bottoni of thc flask. Thcse were filtered off together with some adlierent yellow solid matter, and OII examination proved t o he oxalic avid. T o get rid of t h e o x d i c w i d t h e entire inass was dissolved i l l hot water, froin which H large clop of crystals separated on cooling, the oxalic acid, together with a yellow coloring matte going into solution. T h e crystals t h ~ obtained j were repeatt‘dly CI talliztd wit of boiling water, until t h e y hccanie almost coloi~less. Aftt.r\v:trds, being srriall arid not well defined, they werc eryst,allized out of alc~JhOl,1)enzenc and cliloroforni, but not with ninch grcatei. success. ‘I’hc latter solveiit afforded theni , comliosed of white traiisluceiit Itiaflets, which polarized untler t l i t l microwopt.. (.’onsitleriLbly below ioo’ the crystals begin to sublitne! arid are slowly volxtilized without melting or 1111dergoing decomposition, even when the temperature is wised as high as ~ x J ’ . ‘l’lie product, purified as far :is pos4l)le 1)y repeated crystallization from boiling water, was :iccorilingly transferred to a retort and kept in the air bath at t,he tenipcratnre 1:0”, until :tll thc crystalline substance was sublinied over. Tlicx C I tais thiis obtained were r c d i l y soluble i n hot water, alcoliol, Ixnzcnv and chloroform, but i i i c~ildwitter alniost insolublca.
ACTION OF HYPONITRIC ANHYDRIDE ON ORGANIC BODIEB.
417
On analysis they were found to contain: I. 11. C a r b o n . . ...................... 52.33 53.23 Hydrogen ...................... 3.75 5.08 These figures closely approximate to the composition of dioxybenzoic acid, C,H,(OH),.COOH, the discrepancy being in a somewhat low percentage of carbon. I n order to ascertain whether a different result could be obtained by further purification of the substance, it was once more sublimed, this time a t a temperature of 220°, twice dissolved in boiling water, allowed to cool after each solution, filtered, washed and dried over sulphuric acid. 0.1979 grrn of the substance yielded on combuqtion, 0.3886 g r m carbonic acid, and 0.069 1 grm water, correspondiiig to
C a r h o n . . ....................... Hydrogen .....................
Found. 53.58
3.88
Theory. 54.54 3.89
This would add a fifth to the four previously known of the six possible modifications of dioxybenzoic acid. From three of these, protocatechuic acid, oxysnlicylic acid and the dioxybenzoic acid (1:2:4), it differs both in its melting point and in not yielding a coloration with ferric chloride. It agrees most nearly with the modification, which has heen obtained by Barth and Seithofer*. By heating benzoic acid along with sulphuric acid and phosphoric anhydride to 2 5 0 q in sealed tubes, they produced a disulphobenzoic acid, the potassium salt of which, when melted with pota$h, yielded the modification o f dioxybenzoic acid referred to. But the new modification differs from this body by its not forming a hydrate when crystallized c u t of hot water. It is anhydrous, whilst the acid of Barth and Senhofer in the air-dried state, contains 13 molecules of water. Unlike this acid, which melts with decomposition a t 222O, it does not melt, b u t begins t o sublime a t 1 70°, and may be sublimed without undergoing change, even when the temperature is raised as high as 2.70'. The acid of Barth and Senhofer, wheu heated with strong sulphuric acid, dissolves to a red liquid that deposits agreen powder on the addition of water. I n the case of the new acid, its solution in sulphuric acid is not colored. It forms readily soluble salts with the alkalies, alkaline earths and with lead. Its silver salt, which while somewhat soluble in water, is the least soluble of the salts thus far made, crystallizes in thin transpar-
* Ann.
ClIetti. Pharni,
159,217; 164, 109.
cnt plates with a silky lustre. Unlike the silvcr salt of the acid obtained by Uiirtli and Senhofer, whic:li ( ' ~ J i 1 t : L l I l S 1 mole(~iilL~ O F w,iter o f crystallization, thi It is ;iiihydrij~is. l off. lifterwards tlie thei~inorncter i'ose t o " 8 --"g'-', when i t a p i i i 1)ccame constant, and the reninindei* of t h e oil c8:tinr' ovvr, leaving oiily a very small residue, consisting of a dark retldisli oil t)ehiiid. Goth portions had exactly the same bcautit'ikl tiiit of str;iw-yc~llowcoloi.. H u t the latter, with the coiisi~1eixl)lyhigher hilirig point, was thoiight, to be a differcnt substiiiiw froin t l l c l oil hiliiig a t Z'L'LC, i i n t i l its specific gravity was tlet,eimiiiecl, wliich \\*:is 1. 159. 'l'lie specific gravity of oi~thor~itrotol~rerie is stated to be I . l t i : j , itnrl I,oth portioris of tlie oil thei-cfore were orthoniti.otoluciie. As t h e oil was distilled off with the w:ttcr i n tlie oi.igiiial pi'ocess of the purification, the residue bccainc mure and inorc solid! u n t i l finally, on cooling, the liquid lwcame tilled with eryst,:ils. 'L'hese were puritied b y repeated crystsllization from boiling \rater, i n which the; were readily soluble, uiltil they were :iI iriost ccoloi~less. They were further purified by sublimatioii, the sul,liiried crystals
ACTION OF HYPONITRIC ANHYDRIDE ON ORGANIC BODIE6.
419
melting a t 120°, which melting point, together with the white laniinated appearance of the crystals formed by sublimation, and t h e characteristic: odor given off on heatiiig, proved the substance t o be benzoic acid. Finally there remained behind, after all the oil and benzoic acid had distilled over, a large amount of a very dark colored tarry residue. This was sublimed a t a temperature of about 1lo", yieldink; nearly 10 grms of beautiful light yellow ci-ystals. These were needle-shaped, but clustered together so as t o form feathery or arborescent crystals. Their solution in water was light yellow, staining silk perrnanently of the same color. No insoluble salt could be formed. After repeated sublimation, the melting point of the crystals was 109' to l l O o , and since this is likewise the melting point of paradinitrocresol, C,H,(N0,),0, the supposition first formed was t h a t the new substance was no other than paradinitrocresol. T h e similarity in its dyeing and other properties, and its mode of derivntioii (paradinitrocresol being obtained by the action of nitrous acid on paratoluidine), gave t o this supposition so strong a likelihood that it was abandoned only after repeated analyses. The first two analyses gave: I. Carbon . . . . . . . . . . . . . . 39.26 Hydrogen.. . . . . . . . . . . 2.98 Nitrogen. . . . . . . . . . . . .
11.
39.60
Theory. 42.42
4.24
3.03
14.19
14.14
A portion of the supposed paradinitrocresol, after resublimation, was crystallized out of its solution from alcohol. 0.2113 g r m of this product gave 0.3016 g r m carbonic acid and 0.0678 g r m water, corresponding t o Carbon ................................... Hydrogen .................................
38.92
3.56
Two more analyses were made, with the result of showing t h a t t h e new substance was not paradinitrocresol, C,H,(NO,),O, but dinitro-orcine, C,H(CH,)(NO,),(OR),, which differs from the former only in containing one more atom of oxygen. I n other words, not only had two of the atoms of hydrogen in the toluene been replaced by NO,, but it had been raised by oxidation to the condition of a derivative of orcine. Unexpected as was this result, yet it is fully confirmed, not only by these repeated analyses, but also by those made later npon the constitution of the salts. Comparison with dini t PO-orcine , C ,H (C €I3)(NO,) (OH),:-
420
ACTION OF NTPONITRIC ANHYDRIDE ON O R G A S I C BUDIES,
Carbon
. ... .. . . . . . . . .
IV.
v.
39.09
38.55
4.01
Theory. 39.25 2.90
1:j.09
Dinitro-orcine has already been obtained b y Stenhouse and Groves*, by the action of dilute nitric acid in the cold upon nitroso. orcine; strong nitric acid f o l k trinitro-orcin-. B u t the physical and chemical characters of the I J O I I ~ Jobtained b y Stenlioase and Groves, arc altogether clifferc~tfrom those of this new- modification derived from toluene. I n t h e absence of present krlowle(1ge as t o the relative orientation of the NO, g r o u p i n the t\vo Iwdies, I sfiall designate the former as u,the lattcr as /J-dinitru-orciric.. 't'hc melting point of the forniei-, a5 determined b y Stenhousr aiid Groves is 164O.5, t h a t of the latter is 109" to 110". 'I'hc former crystallizes in deep yellow rhomboidal plates; the latter as bright yellow needles, when prepared by sublimation, and as golden yellow nee(1Iq whcii cryst:tllized out of alcohol. T h e former is alinost insoluble iii cold water, t h e latter is slightly soluble i n cold, vci-y soluble in boiling water. The alkaline salts of wlinitro-orvine :LIY' vel.!- soluble i n water, diflicult to crystallize, and orange-ret1 in ceolor. 'l'iic s m i c is true of the solubility of the corresponding salts uf /j-diriitro.orciiie, but their color is golden yellow. 'l'tie caloiurn anti lead salts of A-dinitroorcine crystallize in yellow needles, the silver salt i n plates. While barium forms with dinitro-oiscine two liydrattvi d t s , one of which i H normal, the other acid, 0-dinitro-orcine forins only otic', and that the normal salt. I t crystallizes in long reddisti-yc.lluw needles, which have the p r o p i - t y not shared by any other of the silts s o far examined, of exploding violently when heated. It ( from alcohol, but not so well as from water, forinirig g Y J l l p S or nodules of sinal1 needles. An attempt was made to form two salts with toluidine, by bringing one and two inolecrilcs of toluidine in alcpholir holution, into combination with one molecule of /j-diiiiti.o-orciiie likewise dissolved in alcohol. T h e salts whic:h were formed in both cases, after recrystallization from alcohol, had the same melting point of 108'. Whilut both crystallized in small yellowish-red needles, that w i t h two molecules of toluidine was somewhat tile lighter in color. F o r this reason, both salts were redissolved in water, i n which they are readily soluble. T h e y crystallized out in needles of the sanie color, b u t ~
.
.
~
*yourn. C % r m . SOL.,1077, 548.
~~
-.
ACTION OF HTPONI'I'RIC ANHYDRIDE ON ORGANIC BODIEG.
421
much larger than those obtained from the alcoholic solutions. T h e melting points of both substances still reinaincd a t 108'. An analysis of that prepared with a solution of two molecules of toluidine, and recrystallized from water, demonstrated that it contained in chemical combination but one molecule, and that both substances were t h e same body, t h e normal toluidine salt of dinitrn-orcine or
C,H,N.C,II,(XO,),O,. 0.1793 g r m of the salt yielded 0 . 3 5 6 6 grrn of CO, and 0.0852 grm of water, corresponding to FOUND.
THEORY.
Carbon 54.24 54.72 Hydrogen 5.28 4.89 9.12 Nitrogen 31.27 Oxygen T h e amide was prepared b y reduction of the p-dinitro-orcine b y means of tin and hydrochloric acid. After complete reduction had been effected, the tin was precipitated b y sulphuretted hydrogen, the stannous sulphide filtered off, and the filtrate evaporated to dryness. T h e amide was left as a dark reddish-brown powder. Attempts made t o obtain it in a crystalline form, b y the use of various solvents and by sublimation, were unsuccewful. I n concluding this part of the subject, it sliorild be mentioned t h a t the aqueous solutions of p-dinitro-orcine and certain of its salts, dye silk a permanent and very beautiful yellow color. I t s ready preparation b y the treatment of toluene with hyponitric anhydride, and its relatively large yield therefrom, may render its practical application in the arts of some future importance. SYLENE.
2 5 0 grms of xylene, aftl:r treatment with hyponitric anhydride in the same manner as the toluene, a t the expiration of a like interval of 5 months, were found to have yielded an abundant crop of large colorless crystals along with some adherent solid matter, and a supernatant yellowish-red oil. No unaltered xylene remained. T h e solid portion, by treatment with successive portions of water, was separated into oxalic acid, which had constituted the colorless crystals alluded t o above, and another white crystalline body with a melting point, A comas determined after repeated crystallizations, of 192'-193'. bustion performed on 0 . 1 5 3 7 g r m of this latter substance yielded 0.3255 g r m CO, and 0 . 0 5 6 6 g r m H,O, from which it appears that its formula is identical with that of phthalic acid, C6H,(COOH), :-
422
ACTION OF HPPONITBIC ANHYDRIDE ON O R G A S I C B0I)IES. FOUND.
THE 0RY.
Carbon 57.75 57.53 Hydrogen 4.09 3.62 38.85 Oxygen T h e oily portion was distilled with water, arid the oil which came over in the distillate was purified by repeated distillation in a cui*i*ent of steam, until its boiling point became constant. This was a t 234', proving t h a t t h e light yellowish-rcd oil thiis obtained, was orthonitroxylene. On rooling, the water in tlie retort deposited crystals, which after being repeatedly recrystallized from boiling water, proved to be paratoluic acid. T h e insignificant amount of reddish solid residue finally left in the retort, was fonnd to consist m e x l y of paratoluic acid with a small amount of oil. PHENOL.
T h e phenol was attacked by hyponitric anhydride with great energy and rapidly converted into a blackish mass. On boiling this with water, and filtering from the carbonized residue, the solution deposited crystals which, on recrystallization, proved to be picric acid. This was'the only Rubstance present; instead of obtaining, as in the case of the substances previously experimented upon, a mixture of nitrified and oxidized bodies. AXILINE.
Aniline was likewise very energetically attacked by N,O,, and converted into a black Aerni-solid mass. When this was treated with hydrochloric acid a portion dissolved in the acid, and was again precipitated by potash. On attempting to sublirne the original nitrated product, a large amount of aniline was distilled off, but no crystalline sublimate was obtained. Another portion was prepared, and a portion subjected t o very careful distillation, the teinperature of the retort being kept a t about 185'. A light red oil was given off a t this temperature, which gradually became darker in color. After several hours the entire mass was carbonized, but no crystalline sublimate came over. Another portion of the raw product was boiled with water and filtered while hot, axid then, becoming turbid on cooling, was again filtered. It yielded a dark red liquid. ThiM was evaporated to dryness, on the water bath, leaving a blackish solid residue. This residue was then rediwolved in water, and agaiii evaporated to di*yness when it had lost most of its tarry properties, though i t did not present a crystalline appearance. On heating, i t
ACTION OF HTPOXITRIC ANUTDRIDE ON ORGANIC BODIES.
423
gave off only a few drops of oil until, the temperature having been raised very slow ; tt) li4', it gave a violent puff and carbonized. Having failed t o obtain from aniline any results by methods similar to those which had proved succesrful with the other substances experimented upon, various portions of the aqueous residue were dissolved in alcohol, ether, chloroform, hydrochloric and acetic acids. T h e chloroform appeared to anvu'er best because i t dissolved the smallest amount of the tarry matter, and from the solution some needles crystallized out. B u t they were in quantity too small t o admit of their analysis, nor was a more successful result obtained when the entire aqueous residue from another portion of the nitrated aniline was treated in like manner. W h a t , however, we had failed t o do with care was apparently accomplished in one instance by accident. A portion of aniline, amounting to about 100 grms, was treated with hyponitric anhydride for a shorter period than usual, a considerable amount of the aniline being left unacted upon. On expelling the excess of aniline by boiling with water, a crop of crystals separated out a t once from the cold aqueous solution. These crystals were repeatedly crystallized out of alcohol, until their melting point became constant a t 12:jo. They were in the form of long needles, with a beautiful dark red color, and contained nitrogen; unfortunately only 0.0707 grin remaining after purification, for analysis. I t gave 0.1883 g r m CO, and 0.05 grm H,O,corresponding to 72.63 per cent. of carbon, and 7.85 per cent. of hydrogen. Such a percentage of carbon could not be brought into harmony with any formula, and it was evident that the analysis \vas at fault. I t is useless to narrate the remaining unsiiccessful experiments. On the supposition t h a t a too long exposure to the hyponitric anhydride had, in all trials except the previous partly successful one, decomposed the niti-o-derivatives first formed, various new portions of the aniline were treated with hyponitric anhydride for ditferent periods, and the resulting products examined, but without success. My object in giving these details, a t such length, is to assist any one who may in the future repeat these experiments. T h e properties and meltinj; point of the body found differ widely from those of any of the nitranilines hitherto obtained, and there is little question of ita being a new substance. ORTHOTOLUIDINE, XYLIDINE, CRESOL.
T h e results arrived a t with these bodies were still less eatisfactory than those obtained with aniline. 100 grms of orthotoluidine (m. pt.,
424
ACTION OF HYPONITRIC ANI1YDKII)E OS O K G B S I C BODIES.
199") were treated with hyponitric anhydride for three hours, when t h e operation was discontinued, tlie toluidine apparently being c o m pletely changed and converted into :i black solid. This pi.oduct was boiled with watw, the soliitioiis aftel, cociling tiltereil and evaporated t o dryness. A purplish-black rcisiduc reriiairicd with sonic rriiiiute tals. rl'his W M trarisferiwl to :i retort, ant1 the ternperatrire ixised very cautiously. So snblirnate c~airieoff below 1 :E", aiid a t this point tlie subst;tnce was tlvcoriiposetl wit Ii a p i i f f , leaving only w i n e carbi-inized matter bchintl. 011 atteinpting t o clissolve out, t ) y the UACL of solvcnts, any i~ryst;illiiie1)odicI.; Iii.ewnt i i i t h e residues obtained from tlit: solution o f otlier p ~ r t i o i i i( i f oithotoluicline siniilarly nitrated, 01' t o carry thciii over. , 1 t l i h t ill:itioii i n a curlwit o f superheated steam, no r c d t s were obtained. 100 grins of xylidirie, after nitration for fvur lio[irs, and 100 grnis of cresol, after nitratioii f b r twelve> hours. wt.i*e converted into blackish-ret1 inasses, wliich were tre:ttt:tl i i i like rti;iiiiier with boiling water, arid their aqueous solutions after filtratiori cv:iporatetl to d r y ness. Dark red residues W E I T obtniric(1 froni bot11 sal~stances,and these iwitlues were dwornposed at l u ~ rtein1,cr;iturt~s\vlien :ittcriipts \vert%rnxle to sul~liniet h e m h'or were any p i ~ d i i c t sobtaiiietl h y the use of solveiits, or by distillation i n a c:uiwnt of sttsani.
2nm R A C ES E Anthracene is converted by tlie action of hypcmitric anhydride into anthraqninone. Along with the nnthraqiiinone i? small amount of red oil is forined, which is best removed by meahai~icalseparation with filter paper, and by washipg with ether. Since, i n every other iri. stance, besides a product of oxidation, some nitro 01'hydroxyl-derivative had been obtniried, it was thought. that a different result might be arrived at by operating upoii it solution of anthracene in glacial acetic acid. 5 0 grms of anthracene, dissolved i n 4 0 0 C . C . of the acid, yielded, after saturation with N,O,, 58 grms of anthraquinone. T h e theoretical amount of anthi~aqiiinonewas 58.3 grnis. A little ret3 oil was formed a t the kame tinie, but no hydroxylated or nitro-derivative.
ACTION OF HYPONITRIC ANHYDKIDE O N ORGANIC BODIES. Y
E.
h
6
z
W
0' 0 h 3 u3
x" ci
0'
E. E.
c-.
425
426
ACTION OF HYPONITRIC S N H P D R I D E ON ORGANIC BODIES.
(‘oxcLcsIos.
By an examination of the accompanying table of prorliwts, it will be seen that in every case except i n thosc of anthracene niitl phenol, oxalic acid was one of the substances formed. T h a t this should have happened with :tnthracenc was not to bc expected, inasmuch as anthracene is convertecl hy direct oxidation into ,anthraquinone. B y an oversight, the f x t of t,he production of oxalic acid from naphthalene was not inentioiled i n the original article, although its isolation and analysis were given a t I t q t h in the original notes. I n the case of cymene, the oxalic acid i 5 enclosed i n hrackets to indicate that it was not isolated. T h e cyniene was c~xaniinedimmediately after nitration, the toluene and xylene not until after several months, during which long interval an opportunity h:d been afforded t o the oxalic acid to separate in cryst:ds. T h e new oxygen derivative, C,B,O, obtained from benzene, i s not puiiaone, @,H,O,. Although in a brief abstract of In)- first article published in the Be,*icshtt der tlticfsch. ! * h e m . Gescllschctft, 13, 1993, this substance is stated to be quinone, j-et this statement is incorrect. It is expressly mentioned in m y original paper, that the composition and the properties of the new substance conclusively establish that i t is not quinone, but a monoxy-derivative of benzent.. T h e most striking phefiomenon connected with the iict,ion of hyponitric anhydride upon the aromatic compounda, is the absence of uncombined water from among the products, and the formation of hydroxylated derivatives. The introduction of the liydroxyl group, in fact, is t o be looked upon as the principal function of hyponitric anhydride in these cases. I t is to be regarded, therefore, as an agent of quite a different sphere of application’ from nitric acid, which, under like circumstances, together with a rertain amount of oxidation, acts chiefly by the introduction of the NO, group, water being eliminated. Not water, b u t nitrous oxide, N,O, is given off when hyponitric anhydride is employed. No nitric oxide was found in the gas after it had acted upon the compound (benzene was the body more especially experimented upon in this connection), while laughing gas was given of i)z great ct6u?iclcr)~ce. This fact, together with the occurrence of the water of crystallization in t h e crystallized oxalic acid, which very slowly separated out of the mother liquid, is t o be borne in mind in attempting to obtain, in a chemical equation, the numerous produc’ts actually formed. In the case of benzene, the following equation would be in harmony with what was actually observed:
ACTION OF HYPONITRIC ANHYDRIDE ON ORGANIC BODIES.
6CeHe
427
+ 13NzO4= ~(CZH,O~.~H,O) +CeH40 +C,H,(NOz) +CeHpOH + C,H,(NO,),.OH +6CO,+ 7N,O.
W h e n nitric acid acts up011 benzene, the reaction takes place in accordance with the familiar equation :
C,H,
+ IINO, = C,H,(NO,) + H20.
But the liberation of N,O, when N,04 acts upon the aromatic compounds, shows that a decomposition must occur represented by N,O, = NzO 0, 0. I n other words, the fact that an uneven number of atoms of oxygen is set free shows that a t the moment of their liberation, one a t least of these atoms must be in its uncombined or nascent condition. And while i t has been abundantly demonstrated that triatomic oxygen cannot oxidize the elements of water into the form of hydroxyl, it has been conclusively shown that nascent or monatomic oxygen can. This is strikingly shown in the oxidation of phosphorus in the presence of water, where the nascent oxygen necessarily set free in the course of oxidation of the phosphorus, not only oxidizes the oxygen present into ozone, but a portion of the water into hydrogen peroxide. So, likewise, if benzene be added to the water in which the phosphorus is undergoing oxidation in partial oxidation with air, the ozone reaction disappears, and under proper conditions a notable amount of plienol is formed. T h e details of this experiment will presently be made public. T h e sequence of decompositions resulting from the action of hyponitric anhydride upon benzene would appear to be as follows :
+ +
(1.)
+ 2N,O, = 2C,H,(NO,) +C,HpOH+N,O+H20+0. + 0 + 0 = CeH40+ H,O.
sCJ&
(2.) C,H,
T h e water thus found appears to have been that essential t o the formation of the crystallized oxalic acid. No uncombined water, as previously stated, was found among the products of the reaction. T h e phenol was a t once and entirely converted into picric acid, a change established by an independent research upon the deportment of phenol itself with hyponitric anhydride. So likewise in the treatment of the toluene, no less than three hydroxyl derivatives were produced-benzoic acid, the new inodification of dioxybenxoic mid, and orcine, which was afterwards converted into the p-dinitro-orcine. I n other words, we have in the first case the conversion of the Ride chain into carboxyl; in the second, this conversion along with t h e replacement of two hydrogen atoms of the nucleus b y hydroxyl; in the third, thb side chain is unaffected, and only the two hydrogen nucleus atoms have suffered replacement.
42s
DmEcrIox OF STARCH SUGAR, EL'c.
Similarly the xylene lost not only one of its two methyl groups, forming paratoluic acid, hiit also both of the members of the side chain with the production of phthalic acid. I n the case of cynliiie? however, the propyl group appentwt to break down so much more readily than the methyl group, that thc latter was protected from the oxidizing action, apd the only hy(lroxyIa~c'(1 dwivat,ive was paratoluic acid. B u t the most striking cxeniplitication of this tendency t o forni hydroxyl derivatives v cxhibitecl by naphthalene. S o t only was the carboxyl p i i p 1~roduced,with the generation of phthalic and oxalic acids (both of which chaugcs might be looked upon as evidence of a siniilwity of action b e t w c n hyponitric anhydride and nitric acid), but the new hydroxj-latetl compound, tetroxvnaphthalerit, C,,EI,(OII,), w:ts formed. In this body n o less than four o f tiit. hydrogon atoms iii naphthaletic :ire replaced by hydroxyl. A t the same time, the diyuinoiie, ClcH40k,was formed, in which four atoms of hydrogen are replaced by oxpgeii. I t is not improbable that both dioxynaphthalene, C,,H,(OH),, and naphthoquinow, (',J-I8OI, Irere first formed and afterwards converted into these higher derivatives. 1 5 i i t of these, and of naphthol and of dioxynaphtlioqiiinone, C ~ ~ I 1 4 0 ~ ~ Ono I l )evidenw 2, could be found in t h e final products.
XLVI.--I)ETECTION OF STARCH Sucan MECHANICALLY XIXED WITH COVMEKCIAL Cas>: SUGAH. B Y P.
C'AS.k.\l.\.Jol
