ACTION OE' A M I N E S O N DIBASIC ALIPHATIC ACIDS.
I233
55 per cent.l of the nitrogen was evolved. Nitric acid2 was found in the solution. Ammonia.-When I cc. of ammonium chloride solution, standardized by 0.1N silver nitrate and containing 0.00613gram ammonia, was treated in a nitrometer with sodium hypobromite a t 742 rnm. and 21.5', (a) 4.66 cc. N, and ( b ) 4.64 cc. N, were obtained-calculated volume was 4.65 cc. N,. Now since urea and ammonia quantitatively evolve nitrogen, since guanidine and semicarbazide evolve two- thirds of their nitrogen, since hydroxylaniine evolves about one-half of its nitrogen, since methylamine slowly evolves its nitrogen, and since urethane almost fails to evolve nitrogen, i t is concluded that, when treated with sodium hypobromite, the mere presence in a compound of the umino group is not a criterion of evolution of nitrogen. T h e ir@uence of other groups in the compound mentioned is a greater factor. If the reaction of sodium hypobromite with these compounds were purely ionic, certainly greater similarity of reaction is expected. However, if there are formed different aggregates as H H H
0.011 j gram-or
(XI
I
I
( a ) H-N-H,
( b ) HO-N-HI
/\
/\
I A
(c)CH,-N-HI
NaO Br NaO Br NaO Br either representing respectively different stabilities, or ease of dissociation, or representing in the same aggregate tendencies to dissociate in more than one direction, a more rational basis of interpretation of these organic reactions is revealed. Studies will be continued along these lines with compounds containing two atoms of carbon. SEATTLE, WASH., June 24, 1909.
ACTION OF AMINES ON DIBASIC ALIPHATIC ACIDS. FIFTH COMMUNICATION ON AMIDIC ACIDS3 B Y J. BISHOP TINGLEA N D S. J. BATES.
Received September 4, 1909.
With the exception of the work on succinic acid, described in the first paper of this series, attention has, hitherto, been directed exclusively to the interaction of amines with phthalic acid and its substitution products. I n the present communication we describe the results which we Cf. with NaOCl, Ber., 20, 1504. All of the other nitrogen-containing compounds failed to give solutions containing nitric acid. The previous papers bearing on this subject have appeared as follows: Bishop Tingle and Cram, Am. Chew. I., 37, 596 (1907);Bishop Tingle and Lovelace, Ibid., 38, 642 (1907);Bishop Tingle and Rolker, THISJOURNAL, 30, 1882 (1908);Bishop Tingle and Brenton, Zbid., 31, 1157 (1909).
I234
ORGAKIC A S D BIOLOGICSL.
have obtained by estending the investigations of Bishop Tingle and Cram to other aliphatic dibasic acids. b y e have examined the behavior of certain amines, usually aniline and ,?-naphthylamine, with oxalic, succinic, fumaric, maleic, malic, citracoriic and tartaric acids. The amidic acids, RNHCO :!: * ::: CO,H, of this series \vhich we have prepared. have been investigated with regard to their ability to transform into imides, R r /
CO \SK, or into amides, IINHCU
\co/
***
CONHII,
by the action of amines of various types. Under conditions in which phthalamidic acids, RNHCOC,H,CO,H, are converted very readily into
imides, C H
’
co ,\cy’‘NR.
the aliphatic amidic acids are quite stable and
even much more prolonged heating, a t higher temperatures than were used with the phthalamidic acids, failed to effect their transformation. I t has been shown by Bishop Tingle and Rolker’ that this condensation to the imide is preceded by the formatioil of a substituted ammoniuiii phthalamidate, RNHCOC,H,COJH,R’, n9lich, under the experimental conditions employed, is generally highly unstable. The question at once arises a5 to why these salts should be so markedly different in this respect from the ammonium aliphatic amidates, RNHCO CO,NH,R. Our nork has shown that their instability is not due to the nature of the groups R and R’ in the amine residues, nor is i t caused by the tendency to form a five-membered ring, because such a cycloid exists both in the phthal- and succinimides. The stability of the fumar- and maleanilic acids proves that the transformation of the phthalic derivatives is not produced by the presence of the double
***
‘ \
C.CO,
1:
linkage in the complex,
\NR, nor can i t be due to any specially
c.co’
/ favorable stereometric arrangement of the amidic and carboxylic radicles
\
a s i n CONHR,
and
\
CONHR, for example.
I!
I1 CO,NH,R’ R’NH 0 C
3/3
/
We may regard the phthalamidic acids, or their ammonium salts, as
\\
C.CONHR
1
existing in the primary phase of the Kekul6 formula,
C.CO,NH,R’
‘ 1.06..
// cat.
A4CTION OF AMINES ON DIBASIC ALIPHATIC ACIDS.
I235
i. e . , with a single linkage between the tertiary carbon atoms instead of the double one shown in the imide formula given above. This linkage would correspond with that of the succinamidic acids, RNHCOCH,. CH,CO,H, which, as previously mentioned, we have found to possess a relatively high degree of stability. Assuniing the validity of these considerations, we are driven to regard the lack of stability of the ammonium phthalamidates as being due to the inherent properties of the benzene nucleus. We hope to test the question still further by extending the investigation to the di-, tetraand hexahydrophthalamidic acids. Oxanilic acid is not changed by heating with ethyl or methyl alcohols, or with toluene, a t IOO', during 35 minutes. Under similar conditions, in presence of aniline, quinoline, pyridine or P-naphthylamine i t forms with each base an ammonium salt. All of these crystallize readily and are quickly resolved into the parent acid and base by the action of either potassium hydroxide or hydrochloric acid. The addition of dilute hydrochloric acid to potassium oxanilate produces a crystalline acid salt,
C,H,NHCOCO,K.C,H,NHCOCO,H. We were unable to prepare oxal-,&naphthylamidic acid by the method described in the literature.' Succin-p-naphthylamidic acid melts a t 184-185'~ not 1g0-1g2 '. It is not changed when heated a t IOOO, during 3j minutes, with alcohol or toluene, either alone or when mixed with aniline, quinoline, or P-naphthylamine, respectively. I n alcoholic or ethereal solution, a t the ordinary temperature, fumaric acid and aniline form the arzi1,ine hydrogen salt, C,H,NH,O,CCH : CHCO,H, melting a t 185'. KO dianiline salt could be obtained. At I 60-1 7 0 O , aniline and fumaric acid yield only phenylaminosuccinphenylimide (phenylasparaginanil) ,
CHz.CO>NC6H,. which, hitherto, c6H,NHLH.codoes not appear to have been obtained from fumaric acid. We were unable to prepare fumaranilic acid by Bischoff's method,2 but we obtained it, without difficulty, from fumaryl chloride and aniline, in ethereal solution. When heated at IOO', with aniline alone, the anilic acid forms phenylasparaginanil, but a t 65 O, in alcoholic solution, aniline does not attack the acid. Maleanilic acid was obtained without difficulty from nialeic anhydride 1 Mitt. Technol. Gmerb. Mzrs. Vienna [ii], 8, 31G (1899). I wrote to Professor Friedlander on ilug. Ist, telling him of this result and asking him if he could supply a n y details regarding the preparation of the compound, or if he mould send a copy of his original paper, which is inaccessible to me. Up to the present (Oct. 11) no reply has been received.-J. B. T. Ber., 24, 2003.
1235
ORGANIC A N D BTO1,OGICAL.
and aniline, by Xnschiitz's \\;hen heated during 3j minutes, a t IOO', the anilic acid is not attacked by quinoline alone, or in presence of a solvent, the same is true of aniline: at 6 5 O , hut a t IOO', without a solvent, aniline converts the acid into plieiiylasparaginanil. Malic acid and aniline, hen mixed and distilled under reduced pressure, form nialeariilic acid and pli~ri~lasparaginanil;the production of this latter substance, in the manner described, appears to be new. We encountered great difficulties in the preparation of inalanilic acid, the method described by .Irppe2 proving to be entirely unworkable in our hands. \i-e finally olitainecl, by a different method, a substance which we think is the anilic acid. 1t melts :Lt I j j3 a& when heated with aniline, a t IOO', forms what is probably a stilt. This melts a t 110'. Arppe's anilic acid is stated to melt a t 14j". The quantity of substance a t our disposal was too small to admit of analysis. Some of the difficulties inherent in the preparation of nialanilic acid are pointed out in the experimental portion of this paper. Pseudoitaconanilic acid was prepared from itaconic acid by a slight modification of Gottlieb's method.3 Tt was not changed a t 100' by aniline alone, or in presence of the various solvents which were employed. At the ordinary temperature, in well-dried ethereal solution, and also a t about 100' without any solvent, citraconic acid and aniline form what is probably anilinopyrotartaric acid, CH,C(NHC,H,) (CO,H)CH,CO,II, melting a t 170-171 0.4 Gottlieb states" that aniline and citraconic acid, a t IOO', form the anilic acid, but we were unable to detect the presence of any of this substance in the products of our experiments. Tartranilic acid was prepared by a modification of Srppe's method,u which consisted in hydrolyzing the lartranil with an aqueous solution of potassium hydroxide instead of employing aqueous ammonia. Tartranilic acid forms s d t s with all tlic amines which we iin.estigated. 111 no case was there the slightest indication of the production of any X-substituted imide, The ciniliize and yui?iol!'m s(7Ifs, melting a t 149-150" and I ~ ~ I ~ Lrespecti\-el?, I " , Tvere ohtaincd a t IOO', although i t is practically certain that, like the ~-,ztrpiitlz~'lamaiie sult, they could be prepared at the ordinary temperature. This last salt melts a t 176-177~ ant1 is formed in alcoholic solution. \Vheii heated a t 180", i t is converted into what is probably tnytu rplz e n j & 9-72 cifiiztiz yldimn ide C, H5X H C0CH (0H ) CH(OH)CONHC,,H,, which melts a t 24.0-242 and is also produced by heating ariil.i?ie tnrtav-,~-nufi~cthylilnll'dute, see below. ~
' Ber., 20,
3215.
".A)LrL., 96, 1 1 1 . 4
Ibid., 77, 284. Schiller, Ber., 18, 1046. Reissert, Ibid., LOC.cit., 1). 2 7 7 . ..i)Z?L.,
93, 355.
21, 1362.
ACTION OF AMINES ON DIBASIC ALIPHATIC ACIDS.
I237
Tartaric acid and @-naphthylaminegive a sniall yield of tartar-@-naphthylamidic acid, C,,H,NHCOCH(OH) CH (OH)CO,H, the purification of which was attended with a considerable loss of material. It melts a t about 180" when heated very quickly, evolves water, becomes solid and then remelts a t 2 2 0 ° , doubtless forming an imide. With aniline the amidic acid yields a salt, melting a t 172-174'. The salt, when melted, evolves water and gives tartarphenyl-P-naphthyldiamide (m. p. 240-242 "), as mentioned above. This behavior is interesting because it is the first example with which we are acquainted, of the formation of any unsymmetrical Ai-substituted diamide in the aliphatic series. Similar compounds, derived from phthalamidic acids, have been described recently by Bishop Tingle and Rolker' and Bishop Tingle and Brenton2
Experimental. Oxanilic Acid-It was found to be desirable to modify in some details the method given by AschanS for the preparation of this compound. After heating oxalic acid ( I mol.) with aniline (2 niols.), the resulting aniline oxanilate is dissolved in the smallest requisite quantity of boiling water, acidified with a little less sulphuric acid than Aschan specifies, and the liquid allowed to cool. The mixed precipitate of aniline oxanilate and oxanilic acid was removed, washed with cold water, dried in air and the anilic acid extracted by means of hot toluene. Aniline oxanilate melts indefinitely between 140-16o0 according to the rapidity of heating. On account of this fluctuating melting point and because its appearance is similar to that of oxanilic acid, there is some difficulty in distinguishing between the two substances, the mixed melting point test being, of course, indecisive. We found that, on the whole, the most convenient method was to fuse the material, either directly over a flame or in an oil bath. The acid is not chemically changed by this treatment and, after fusion, i t dissolves readily in warm water. The aniline salt, on the other hand, forms oxanilide when melted and this dissolves with difficulty in hot water. Oxanilic acid is not affected by heating during 35 minutes, a t I W O , with ethyl or methyl alcohol, or toluene. Under similar conditions, andim transforms it completely into aniline oxanilate. With quinoline the acid forms the quinolilzium sa&; colorless crystals melting a t 122-3O. I t is readily soluble in hot water and in alcohol, more sparingly in chloroform, ether, or cold water. From any of these solvents the salt may be deposited as a yellow oil, which after a time changes to the white crystals. The salt is most conveniently purified by allowing its alcoholic solution to evaporate spontaneously. With a n aqueous solution of potassium hydroxide the salt liberates quinoline whereas hydrochloric acid precipitates oxanilic acid from it. Pyridinium oxadate is prepared in a similar manner to the quinolinium compound. It is deposited in colorless crystals, melting a t 132-133~. I t dissolves readily in hot alcohol or water, more sparingly in benzene, and is insoluble in ether. Hydrochloric acid precipitates oxanilic acid from it and an aqueous solution of potassium hydroxide liberates pyridine. ,0-Naphthylammonium oxanilate, obtained in a similar manner, forms pink crystals, melting a t 1 5 1 ~ . It dissolves in alcohol or water, but is less soluble in toluene
* THISJOURNAL, 30, 1882 (1908). a
Ibid., 31, 1157 (1909). Ber., 23, 1820 (1890).
ORGAXIC .\ND BIOLOGICAL.
123s
and insoluble in ether. .i niixture of i t with an equal quantity of oxaiiilic acid melts With hydrochloric acid a n d potassiilm hydroxide. respectively, i t bea t 135-rjo'. haves like thc other salts. Potassizwt ii?,dr.ogi'ii o r n ~ i l u f c ,C,,H,SHCOCO,~,C,H~SHc~COpH, was prepared by adding dilute hydrochloric icid slonly ~ I .J: wturated aqueous solution of potassium (jsanilate, until no iuitiler prcc pitate is formed. The salt was then dried and extracted with rtlier t o remove :niy rr:ices of oxnniiic acid. I t dissolves readily in alcohol o r \Later :?xi its su1i:tions '!IT:icid to litrnus. LYitli hydrochloric acid in excess it forins oxmilic nciil. Analysis showed that i t !i:ttl tlie coinposition give11 :i!mve. 'l'he itniiiioniiiiii salts describctl alxi\-c were tlie only substances which we could tion of the :imines ntid uxanilic acid : nu ir.ice o f a n y imide,
1
cO> CO
SK,coultl be discovered.
O r a l z c Acid and f-SuPlitli~lunti~l.e.--X considerable number of experiments were made, under varyitig condiiions, in order to prepare osal-,3-naphthylamidic acid, C,,H,?;HCOCOpH, but without success. The compound has been described by P. Fried!Bnder, Heilpern and Spielfogel' as being produced at 140-1 j o o , from crystallized oxalic acid and #-naphthylaniine. Cnfortunately their original paper is not accessible to us. S7rccinic Acid nizd ,9-Naplzthylo?ni?w.--A good yield of succin-P-n3phthylamidic acid was obtained by Pellizzari and Matteucci's method,z which consists in heating the mixture of acid and base a t 2ooo, hydrolyzing the resulting imide with potassium hydroxide and acidifying the solution. Our preparation of the acid melted a t 1841S,5 O, thus confirniing the observation of A u w e r ~whereas ,~ the Italian chemists give the melting point as being r g o - ~ g ? ~ . ~ The acid is not changed by heating, a t IOOO, with aniline, quinoline, or 8-naphthylamine, in presence of alcohol, or toluene, during 3 j minutes. Fzmaric Acid aitd Aniliite --These substances combine in alcoholic or ethereal solution, nt the ordinary temperature, giving aniliue hydrogen fuiwarnte, HCCO,NH,C,jH,; I
I
H0,CC colorless crystals, melting at 1 8 5 ~ . I t dissolves readily in warm water or in alcohol, is less soluble in benzene and only slightly $0 in ether. N : found, 7.13; calculated, G . 7 per cent. 'CYhen added to an aqueous solution of potassium hydroxide or of sodium carbomate, aniline is liberated from the salt and fumaric acid iq produced by the action on i t of hydrochloric acid a t the ordinary teniperature. By treating fumaric acid with two molecular proportions of aniline, under the conditions described above, half the aniline remained uncombined and the remainder formed the monoaniline salt. \Then heated during 30 minutes, a t 160-170°, fumaric acid and aniline ( I or 2 niolecules) form only phenylasparaginanil, which does not appear to have been pre. pared previously from fumaric acid. According to Bischoff ,, fumaranilic acid is produced by hydrolyzing fumaranilide, C,H,NHCOCH : CHCONHC,H, with alkali. We employed both aqueous and alco-
Mitt. Technol. Gewerb. MZLS.Vienna [ii], 8, 316 (1899). Ann., 248, 159. a
Ibid.,
4
LOC.
292,
190.
cit.
t i e r . , 24,
2003.
ACTION OF A M I N E S ON DIBBSIC ALIPHATIC ACIDS.
1239
holic solutions of potassium hydroxide, under varied conditions of concentration and temperature, but failed entirely to obtain any of the desired acid. The following method, however, gave the acid in fairly good yield. Aniline is dissolved in ether and the solution added gradually to fumaryl chloride, in the same solvent. After removal of the ether, fumaranilic acid is extracted from the residue by means of warm water. When heated a t 6 5 O , during 35 minutes, with alcohol or with an alcoholic solution of aniline, fumaranilic acid is not changed, but with aniline alone, a t IOOO, phenylasparaginanil is produced. Maleic Acid and Aniline.-Maleanilic acid, C,H,NHCOCH : CHCO'H, was prepared, without difficulty, by Anschiitz's method,' from aniline and maleic anhydride, in ethereal solution. It is not necessary to use absolute ether, as Anschutz states, although the ether should be of good quality. When heated a t IOOO, during 35 minutes, the anilic acid is not changed in presence of alcohol (98 per cent.), benzene, or toluene, nor in that of quinoline alone, or mixed with one of these solvents. A t 6 j 0 , during the same interval of time, aniline alone, or in solution, is also without action on the acid, but a t IOOO, during 35 minutes, without any solvent, aniline and the acid form phenylasparaginanil. Alalic Acid and Aniline.-When these substances were mixed and distilled under reduced pressure, we obtained, in addition to maleanilic acid, phenylasparaginanil, the formation of which, in this manner, has not hitherto been recorded. Malanilic acid has been described by Arppe,%who prepared i t by hydrolysis of the anil with aqueous ammonia. I n spite of numerous efforts, under varied experimental conditions, Me were entirely unsuccessful in obtaining any of the acid by this method. No better results were produced by the use of barium hydroxide as the hydrolyzing agent, but by warming the anil with a concentrated aqueous solution of potassium hydroxide, then cooling thoroughly and adding the calculated quantity of hydrochloric acid, a small portion of what is probably malanilic acid is deposited. It is necessary to use rather highly concentrated solutions and to evaporate the liquid somewhat, after acidification. The difficulties attendant on the preparation of malanilic acid are very considerable; they arise partly from the fact that aniline and malic acid, or the anhydride, may react in several different ways which, in some cases, may give rise to stereoisomeric derivatives, so that in any event the yield of a single homogeneous product would be relatively small. Difficulties of another order are due, as Arppe points out, to the ready solubility of the anilic acid in water and to the fact that i t is hydrolyzed by dilute mineral acids both a t the ordinary temperature and when warmed. Our product was obtained in such small quantity that we do not consider i t necessary to give our method of preparation in greater detail because we do not regard i t as being satisfactory. The substance melted a t 1 5 5 O , not 1 4 5 O as Arppe states, but we failed to obtain enough for analysis. At IOO', with aniline alone, it forms what may be an aniline salt, which melts at 1100.
Itaconic Acid and Aniline. Preparation of Pseudoitaconanilic Acid.-Pseudoitaconanilic acid was prepared essentially by Gottlieb's method.s Itaconic acid was heated with aniline ( I mol.), a t 100-150~,during 20 minutes. The product was powdered, washed with ether and then boiled with water to remove any traces of citraconic and itaconic acids. The yield was good.
Ber., 20, 3215. 96, III.
a Ann., a Ibid.,
77, 284.
ORGAXIC AKD BIOLOGICAL.
I340
\\:hen heated a t x m 0 , during 35 minutes, witli aniline alone, or in solution of nitrobenzene, toluene, or alcohol (,io I'er ccrit.), liseudoitaconanilic acid undergoes no change. C i t r e c o ~ i c A r i d u i i d 14wzlii2~'.- - \\-l!en \wll-dried ethereal solutions containing and aniline are mixed, n substmce equimoleculnr proportions of c i u x o n i c ~tnliydr~dc is deposited xhich, after purification, melts at i j o - r ; ~ " . I t is soluble in a n aqueous solution of sodium carbonate, is reprecipitated by acids and dissolves xithout tliliiculty in nlc~lio! 01- in < a r m cliloroforni. ,..( It i :le compcmiid reduces silrer nitrate. c : 'l'lie reis also prcpareti b y heating atiiiiiie anti citraconic acid a t :! littic : L ~ J ~xoo5. sulting product is warnied \\ith a n aqueuus solution ut-' potassium hydroxide :!XI the clear liquid acidified rvith Iiyclrochloric acid. .\ccording to Gottlieb' this procedure should give citraconnnilic acid, but we viere unable to detect the presence of an? of that substance in the products u i the reaction. Our comp(mid (in. 11. I ; I ) - I 71") is prohably anilinopyrotartaric acid, CH,C(SHC,,H,) (CO,I-I)CH,Cc),H. \Ye were sticcessful in preparing some citraconanil by Gottlieb's metliod.' Turtu~icA c i d o i i d il?tzliix--It n'as found to be desirable to modify Arppe's method' fur the preparation of tarlranilic :wid. Tartaric acid and aniline, in equimolecular ~, .i or 4 hours. The product was hydroproportions, nere heated :it x ~ o - ~ . i oduring lyzed by xvarrning n.ith an aciileous so1utic)ti of potassium hydroxide and tlie anilic x i d preciIJitated from t h e clear solution by acidification v i t h hydrochloric acid. I t is decolorized by means of piirified anitiial ch:ircoal a n d recrystaliized from water. 'l'lie yield is rather poor. \\'hen treated with amines, tartrnnilic acid forms salts; in no case w:ts any tendency shown to pass into :in imide. .-1nilitze tavtm)zzlate, prepared a t I O O O , in alcoholic ( , j c > per cent.) solution, is deposited in colorless crystals, melting :it 149-1joO. Q W ~ J Z O Zinizim tartranilate is prepared in a similar nianner ; colorless crystals, melting a t I ~ i j 1 3 0 ~ . It is not soluble in ether, b u t dissolves in nater. There can hardly be any d o u b t that these salts could be preparecl a t tlie ordinary temperature if it were desired ; we heated their components because of the transformation tests which were being conducted. \\lien treated nit11 hydrochloric ncid each salt precipitates tartranilic acid, whereas with an aqueous solution of sodium carbonate the salts liberate tnrtvuitzlafe is prepared from aniline and quinoline, respectively. ,~-i~e~htiii,Z~nzivie the acid and amine, a t the ordinary temperature, in alcoholic solution, and forms colorless crystals? melting nt I j6-1:7~, it^ dissolves readily in hot x i t e r , more sparingly in cold water and in alcohol. \T.lieii inixeil with tnrtranilic acid, the melting point of the salt is lowered considerably. t1:ater is evolwd if the salt is heated a t ISo'; the residue cunsists of ii ~ O J I Z ~ O I L ~ Z which rnclts :It ~ 4 o - q i 0and is also formed from uniliw tu. see below. Tartaric A c i d u d ~-.\'LTnpiifl/q /uminc.---.X number of attempts xere nmde t o 1mpare faviau-t?-mpiitiz~durnidl'i. &, C ,I3 ,SHCOCH (OH)CH (0H) i t w:is obtained, in sn:all cjuantity, b y the following process: ;3 inol.) and tartaric acid (1';; ~nols.)nere heated a t x8o-zoor', titi powdered product n ~ i boiled s during 30 minutes with excess of R coriceiitr:ited nqueiius solution of Ilotassiutii hydroxide, the liquid filtered while hot, then :illowed to cool and filtered again. Unless this is done a resin which is prescwt will c:it~seit g o d deal (,i trouble hy stopping the pores of the filter paper, The cle:!r filtrntc is n o \ v :icitliiied with hydrochloric acid, which precipit:ites :L black gummy ii>ateri:iI. 'This w:is rt'moved and extracted witli Ijoiling vvnter; the solutioii, wheii ciild, depo::ils il brown Anti., 77, 2 7 7 . Ibid., 93, 355.
~
ACTION OF AMINES ON DIBASIC ALIPHATIC ACIDS.
1241
substance, which was extracted with a hot aqueous solution of potassium hydroxide The alkaline filtrate was boiled with animal charcoal and the amidic acid precipitated from the clarified liquid by means of hydrochloric acid. Under these circumstances the yield is, of course, quite small, and as our material was not absolutely colorless, we decided to study its reactions and not attempt to purify i t further for analysis. The amidic acid melts a t about z z o o under ordinary circumstances, but when placed in a bath previously heated to 18o-1Sj0, the acid melts immediately, evolves water, resolidifies and then melts about zzoo. This substance (rn,p. 2 2 0 ~ ) is therefore the /3-nafihthylzmide The amidic acid dissolves readily in an aqueous solution of sodium carbonate and it has an acid reaction towards litmus; i t is also soluble in hot water and in alcohol. This latter solution, when mixed n i t h a similar one of aniline ( I mol.), forms the aniline salt; colorless crystals, melting a t 172-174~. This salt evolves water when it is fused and the residue consists of the same comPound (m. p. ~ ~ O - Z ~ I Owhich ) is formed under similar conditions from P-naphthylamine tartranilate (see above). The two materials were identified by a mixed melting point determination. When fully purified the compound is obtained in colorless crystals, melting a t z40-z4z0. It dissolves readily in pyridine, b u t more sparingly in alcohol and is insoluble in hot water or in a n aqueous solution of potassium hydroxide. When melted i t does not evolve water nor an amine. I t s methods of formation and its properties show that the compound is a dianzlide, probably, C,H,NHCOCH(OH)CH(OH)CONHC~oH,, though it might, of course, be the anhydridc,
C,H,NHCOCHCHCONHC,&,. \/
0
Summary. I. The action of various atnines on a number of dibasic aliphatic acids, and on the N-substituted amidic acids derived from them, has been investigated. 2. The aliphatic amidic acids, RNHCO CO,H, behave quite differently from the corresponding compounds of the aromatic series. j. With the aromatic compounds, amines, in general, form N-substi-
***
tuted imides,
-co 'NR, -co/
whereas with the aliphatic conlpounds they
either fail to react or else they produce well defined salts which are relatively stable. 4. The cause of this difference in behavior appears, a t present, to be ascribable only to the inherent nature of the benzene nucleus, whatever that may be. j. In connection with furmaric and maleic acids, attention may be called to the ease with which aniline adds to the double linkage. 6. We were unable to isolate a dianiline salt from any of the dicarboxylic acids which we investigated. 7 . From aniline tartar-/3-naphthalamidate and also from $naphthylamine tartranilate (tartarphenylamidate) we prepared what is probably an unsymmetrical diamide. I n this reaction these acids resemble similar compounds in the phthalic series.
ORG \SIC AND BIOLOG1C.G.
1?13
3. IVe have prepared a consitlei-able number of new compounds and we ha\-e devised iinpro 1 methods for obtainiiip certain other substances. ,+ 1 tie work will be continued i l l this lalioratory during the corning acatleniic year. 3rChfASTER c N I V E R S I T I .
TOROSTO, CANADA .
. .
[~ON'I'RIBCTIOX I.'RO.\l THE: BURBALIOF CII6hllSTK'I-.
I.. 5 . DEFT.
THE HYDROLYSIS OF SALICIN BY THE ENZYME
OF AGRICCLTURE.]
EMULSIN.
B Y C. S. H U D S O S AS11 H. S . P.41SE.
Received Septeniber
20,
1909.
In aqueous solution salicin is hydrolyzed by strong acids to glucose and salicyl alcohol according to t.he equation, C,,H,,O, i- H 2 0 z- C,,H,,O, -i C,H80,. (Salicin) -$- (water)
. :
(glucose)
-+ (salicyi alcohol.)
I t has been fouiid by A. X. Soyes and Hall' that the rate of this acid hydrolysis follows the law of uniniolecular reactions. The same hydrolysis can also be accomplished by adding to the salicin solution a little of the enzyme of almonds, called emulsin, b u t in this case it has been stated 1)y Iieriris and other investigators that the rate does not follow a t all the unimoleculnr laiv. A\s this statement that the eiizymotic hydrolysis of salicin fly emulsin does not follow the usual laws of chemical dynamics has passed unchallenged for niany years it has lieen widely accepted as correct. hgainst such a conclusion it is to be said that the glucose which is liberated from salicin by the action of emulsin is doubtless 2-glucose because emulsin hydrolyzes only the ,$glucosides. and /?-glucose has a rotatory power of zoo,init Henri, in his work, assumed that the glutose hart its usual specific rotation. 5.-''. His polariscopic measurements of the rate of the enzyniotic hyilro!ysis are accordingly incorrect, for he made no corredion for the mutarotation of glucose. I n the hydrolysis by acids. as studied by A , .1.Soyes and Hall, this second reaction, the mutarotation of glucose. does not affect the estimation of the extent of the hydrolysis from the polariscopic readings because the strong acid and the high temperature (95") employed make the rate of the mutarotation instantaneous in comparison with the rate of the hydrolysis. b u t in the hydrolysis by emulsin the polariscopic readings do not give the real extent of the hydrolysis unless a considerable correction is made for the mutarotation of the freshly liberated glucose. The case is very similar to the hydrolysis oi cane sugar by the enzyme invertase, in which reacI
Piria, -4nn., 56, 3;. 2. physik. C'lievz., 18,240-4 (1895). Lois gd1zdrde.i. d e l'action des diastases, p.
102
