SALTS OF H&LIANTHINE.
I573
bromic acid molecules. In the case of alkyl substitutions, this equilibrium of forces is disturbed so that molecular combination can take place. MONTREAL, CANADA.
.[CONTRIBUTIONFROM THE CHEMICAL LABORATORY OF THE UNIVERSITY OF WASHINGTON.]
SALTS OF HELIANTHINE. BY C E A ~ L SR. ~ STARK AND WLLLIAYM. DEEN. Received June 19, 1918.
From recent studies by one of us with methyl orange’ and with other colored solutes,2 the conclusion was drawn that color changes in solutions are largely or wholly independent of ionica concentrations. An hypothesis, interpreting such color changes and embracing the following propositions,‘ was indicated: ( I ) The colored solute forms additive compounds with acids, with bases, or with “indifferent” solvents. (2) Solutions of such additive compounds are more or less transformed by the solvent, yielding either simple chromoisomeric equilibria or polychromic equilibria. (3) The intrinsic susce9tibility of the additive compound to the transforming influence of the solvent is the important factor of color changes in solutions. (4) Heat6 and probably other physical conditions have secondary influences on color changes. This paper will concern itself largely with the first proposition-that the colored solute forms additive compounds. It will be shown that helianthine forms salts xvith great ease and that all of these salts can be interpreted as additive compounds. Prior to this only salts of sodium, ammonium, pyridine,6 and hydrochloric acid7 have been described. Thispaucity of described salts is remarkable, when it is observed that helianthine forms salts with the readiness of a strong acid, uniting with all classes of bases whether organic or inorganic. Owing to its amphoteric nature, helianthine also forms salts with acids, but it was found that these salts cannot be prepared pure’ in aqueous solutions. However, if the isomerizing influence of water is avoided, that is, if anhydrous conditions are observed, violet-red salts, compounded THISJOURNAL, 3% 1348, 1377 (1917).
* Ibid.9
3 6 , 8 4 6 (1914); 39, 1338, 1381, 1392, I399 (1917).
IGd.9 39, 1357, 139’4 1396 (1917)1bid.p 399 1376, 1380, I403 (1917)1bid.B 36,845 (1914); 39, 1374, 1391 (1917). 6 Hantzsch, Ber., 46, 1538 ( 1 9 1 3 ) . 7 Hantzsch, Ibid., 41, 1192 (1908).
’
1574
CHARLES R. STARK AND WILLIAM M. DE”.
of so weak acids as phenol, the cresols, etc., can be prepared with ease. These salts also were found to be additive compounds. Salts of helianthine, prepared in aqueous solutions with inorganic bases always contain water of crystallization, and always two molecules of water t o one molecule of helianthine. In other words, such salts of helianthine alwaj-s possess the following forms. C14HI4N3SO3M.2H2O; (C14H14rUT3S03)2M.4H?O;( C ~ ~ H ~ I N B S O ~ ) From ~ ~ ~ .these ~ H ~types O . it is observed that helianthine always unites with all of the base, plus one or more molecules of water. If we assume the following structure for yellow helianthine ( C H ~ ) ~/-N\)
1\; =
N ./ ,-,--SO-\ ~H
it is easy to understand how two molecules of water are always present with each molecule of the htlianthine, as showed in the formula HO
OH
(CHa)?N
/\
HO
OH
Interesting facts are brought out in connection with the color of helianthine salts. First, helianthine salts compounded of ammonia or of volatile organic bases when heated give free helianthine. This was observed by Hantzsch with the pyridine salt. Second, those containing the colored ions Cr,”’ Cu”, Co”, Ni”, Fe” and Fe”’ give no evidence of the presence of these ions if they are judged only by their color. All of these helianthine salts are practically identical in color and this color is almost uniformly that of methyl orange (sodium helianthate) . Third, when dehydrated, all helianthine salts containing the bivalent and trivalent metals, but not the monovalent elements, tend to form the color of helianthine itself. This color transformation is satisfactorily accounted for by the following indicated dehydrations and isomerizations : HO
OH
HO
OH
/-\NR2
’>
\-/ I10
OH
HO
\
/I
R2r\;
OH
/\--NH-N
= N--”--/\
1
1
‘
1
=/\
I
,\/ \ I1 0 - __ s (1 -\ I - 0 - S - - - 0 ------?;Rl --
I
/_-_._I --..o-
0
.
and 9.88.
Chromium helianthate.-Gold-brown
10.00.
Found: Ca, 5.33, 5.34;
rhombic plates.
Calc. for (C14H14N3S03)3Cr.6H~O: Cr, 4.85; HpO, 10.08. Pound: Cr, 4.74; HzO, 10.19.
Cobalt helianthate.4old-red hexagonal and rhombic plates. Calc. for (Cl4Hi~aSO3)~Co.qHzO: Co, 7.95; HzO, 9.99. Found: Co, 7.83; HtO, 9.88.
Copper he1ianthate.-Light
gold-brown rhombic plates. Calc for ( C ~ ~ H I ~ ~ T ~ S O J ) ~ CCU, U . ~8.54; H * OHpO, : 9.46. Found: Cu, 8.72; HBO,
9.15.
Ferrous he1ianthate.-Gold-brown
rhombic plates.
Calc. for ( C ~ ~ H ~ ~ N & O & F ~ . L Fe, + H7.58; ~ O : IIzO, 9.79. Found: Fe, 7.68; Hz0, 9.22.
Ferric he1ianthate.-Red-gold
irregular and rhombic plates.
1 Though given in the literature, the composition of the ammonium salt is not described.
I577
SALTS OF HELIANTHINE. Calc. for (Cl,H14NaS03)sFe.6HzO: Fe, 5.19; HzO, 10.04. Found: Fe, 5.18, H20, 10.83.
Lead he1ianthate.-Brown
5.21;
masses and irregular plates.
Calc. for ( C ~ ~ H ~ ~ N ~ S O & P Pb, ~.~H 23.33; Z O : HzO, 8.12. Found: Pb, HzO, 7.99.
Magnesium he1ianthate.-Red-gold,
23.92;
hexagonal and rhombic plates.
Calc. for ( C ~ ~ H ~ ~ N ~ S O ~ ) ZMg. M ~ .3.45, ~ H ZHzO, O : 10.22. Found: Mg, 3.44; HzO, 10.17.
Manganese he1ianthate.-Large, plates.
light red-gold, irregular and rhombic
Calc. for (ClrH14NsSO&Mn.4H~0:Mn, 7.48; HzO, 9.80. Found: Mn, 7.34, 7.50; HzO, 9.18, 11.32.
Silver he1ianthate.-Dull
brown-red needles.
Calc. for C ~ ~ H I ~ N & O ~ AAg, ~ . ~24.06; H ~ O HzO, : 8.04. 8.24.
Sodium he1ianthate.-A cqktallization.
Found: Ag, 23.98; HzO,
stock sample contained only a little water of
Calc. for C14H1~N&30~a.zH~0: HzO, 9.92. Found: HzO, 1.41.
Nickel he1ianthate.-Light
gold-red hexagonal and rhombic plates.
Calc. for (C14HirNsSOa)zNi.4HzO:Ni, 7.94; H20, 9.75.
Found: Ni, 7.97; HzO,
9.66.
TABLE~.-SOLVBILITIES AND MELTING POINTS. Heated. , 1000 cc. HzO. Colors or Does 7 decom- not Melts. Salt. Hel. poses. melt. 0.092 0.08 2 0 0 ' 280' . . . . . 6 . 0 0 . . . . . . . . 225' 280' 0.201 0.15 280' . . . . . 0 . 0 7 296' 296' 2900 0.I77 0.15 290' 0.176 0.15 270' 270' Solubility
Composition.
Salt of:
Al.......... HelsA1.6HzO "4.
.......
Ba. . . . . . . . . Cd . . . . . . . . . Ca . . . . . . . . . Cr .......... c o......... cu. ........ Fe" ........ Fe "........ Pb . . . . . . . . . Mg ......... Mn ......... Ni .......... K .......... Ag . . . . . . . . . Na ......... Sr ..........
u.......... Zn ..........
Hel.NHa.zHz0 HelSBa4 H ~ 0 HelzCd.qHs0 HeltCa.qHs0 HelaCr.6HzO HelzCo.qHz0 HelzCu.qHz0 HelzFe.qHz0 HelaFe.6H~O HelzPb.4Hz0 HelzMg.4HsO Hel&Xn.qHpO Hel~Ni.4HpO H~.K.zH~o Hel.Ag.zHz0 Hd.Na.nHp0 He4Sr.qHzO HelnU.4HzO Hel~Zn.qHz0
0.036 0.03
280'
280'
2900 300°
0.122
0.10
0.109 0.118
0.IO
.... ....
0.10
280°
0.111
0.08 0.03
0.035 0.060 0.072
0.05
4.368
0.06 3.50
0.292
0.20
..... ....
280'
....
brown bronze-brown gold-brown bronze-brown purple-brown bronze-brown purple-brown gold-bronze
. . . . 3oO0 black-brown
. . . . 2240
0. I O
....
300 O
2500
280'
0.098 0 . 0 8
brown-gold
gold-brown brown bronze-brown
zooD 230'
0.300 0 . 2 5
0.126
209'
300 O . . . . 300 ' 267 ' 280' 270" 280' 275 ' 235
Color. Heated 120".
.... ....
orange brown 241' bronze-brown
1578
CHARLES R. STARK AND WILLIAM M. DE”.
Potassium he1ianthate.-This salt formed a blood-red, ropey colloidal solution that filtered with great difficulty. The crystals were orange hexagonal plates. Calc for C I ~ H I ~ K & 213~0 ~ O ~ KK,
IO
Strontium he1ianthate.-Brilliant
3 1 , HzO, 9 69
Found. K,
HzO, z
25.
orange rhombic plates and needles.
Calc for J C ~ ~ H L ~ N S S 4H20.Sr, O T ) ? S ~ 11 41,H * 0 , 9 38 HzO, 9 01 and 9 24
Uranium he1ianthate.-Orange-red CdlC
IO2 2 ,
Found Sr,
I I 25
and
II
44;
rhombic plates.
for ( C I ~ H L ~ K T ~ S 4H20. O ~ ) ?U, U 2 j 9 3 , HrO, 7 83
Found. I‘,
27
04; H20,
8 84
Zinc helianthate.4old-brown rhombic plates. Calc for (Cl4HIIN1SO3)2Zn 4H20.211, 8 9 8 , H20, 9 90
Found Zn, 8 9 9 : H20,
9 67
Salts of Organic Bases. ilniline he1ianthate.-Gold-orange prismatic flakes and needles. Calc for ClrH15NsSOa CsH,N S, 8 05 Found. S,7 68 Benzidine he1ianthate.-Gold-brown irregular and rectangular plates and prismatic needles. Brucine he1ianthate.-Orange prismatic needles. Calc for C ~ ~ H ~ ~ N Z O ~ C ~HzO ~ H IS,I N4~4S7 ,O HzO, ~ Hz0, 1.69.
Cinchonidine he1ianthate.-Light plates.
2
52
Found: S,
4 74;
yellow prismatic needles and irregular
Calc. for CmHzzNzO C~HibN3S03.S, j 3j
Found. S, j,74,j 74
Dimethylaniline he1ianthate.-squimolecular quantities of helianthine and dimethylaniline gave no yellow color or apparent chemical change on standing for one month. On adding water and shaking, yellow crystals were formed immediately. After recrystallizing from hot water, long needles and hexagonal plates were obtained. Methylaniline helianthate. - Thin, gold-brown prisms and rhombic and hexagonal plates. Morphine he1ianthate.-Bright orange irregular plates and sheaves, and wart-like masses of prisms. Calc. for CMHI~N~SOB CllH19N03. S, 5 43. Found: S,5 40, 5 60. a-Naphthylamine he1ianthate.-Dull-brown needles. Calc. for C ~ ~ H I ~ N \ I T ~ S OC ~ .I C ~H ~O I ~HN~~NS 6.8O01 ~ , Found. C M H I ~ N ~ S68.00. O~,
@-Naphthylaminehe1ianthate.-Brown-yellow thin irregular plates. Phenylhydrazine he1ianthate.-Orange needles and rectangular plates. Calc for CMHISNSSO~.CSH~N~: S, 7 . 7 3 Found. S, 7 8j
a-Picoline he1ianthate.-Dark plates. Piperidine he1ianthate.-When
brown-red rectangular and octagonal an ether solution of piperidine was
I579
SALTS O f HELIANTHINE.
treated with helianthine, the violet-red color of the latter, during a number of weeks, was gradually replaced by bright orange, coarse rectangular crystals of the salt, From hot water, octagonal and irregular plates were obtained. Calc. for C ~ ~ H I ~ N ~ S O ~ . CS,~ 8H. 2I2I.N :Found: S,8.19. Quinine he1ianthate.-Orange amorphous masses. Calc. for C ~ ~ H ~ ~ N ~ S O ~ . C :ZS,~ 5.09. H Z ~ NFound Z O Z: S, 5 . 1 3 .
Quinoline he1ianthate.-Orange-red
prisms and octagonal plates. Calc. for C~~H~SN&~OI.CYH~PVI: S,7.38. Found: S, 7.42. Strychnine he1ianthate.-Gold-orange prisms and rectangular and irregular plates. Calc. for C ~ ~ H ~ ~ N ~ S O ~ . CS,*5.02. ~ H ~ ZFound: N Z : S,5.43, 5.25;HzO, 0.8. o-Toluidine he1ianthate.-Orange-red prismatic needles. Calc. for C14Hl6N&3O3.C,H~N: S,7 . 7 7 . Found: S, 8.38. m-Toluidine helianthate.-Gold-yellow needles and irregular plates. Helianthine phenolate.-Dark purple prisms. Calc. for C ~ ~ H ~ ~ N ~ S O ~ . CS, G8.03. H ~ OFound: H: S,7.54. TABLEII.-SOLUBILITIES AND MELTINGPOINTS. Solubility 1000 CC. Hz0. 7 -
Salt of:
Salt.
Aniline. . . . . . . . . . . . . . 0 . 2 6 2 Benzidine. . . . . . . . . . . 0 . 0 8 2 Brucine. . . . . . . . . . . . . 0.245 Cinchonidine. . . . . . . . 0 . 1 9 6 Dimethylaniline. . . . . . 0 . 7 0 0 Methylaniline. . . . . . . . 0 , 5 4 1 Morphine. . . . . . . . . . . 0 . 4 0 0 a-Naphthylamine.. . . 0 . 1 3 2 p-Naphthylamine. . . . 0 . 1 0 3 Phenylhydrazine.. . . . 0 . 1 3 5 a-Picoline . . . . . . . . . . . 65.300 Piperidine. . . . . . . . . . . Quinine . . . . . . . . . . . . . 0 . 1 8 5 Quinoline. . . . . . . . . . . . 0 . 8 5 4 Strychnine. . . . . . . . . . 0 . 4 8 1 m-Toluidine . . . . . . . . . 0 . 1 6 2 o-Toluidine . . . . . . . . . . 0 . 2 7 0 .... Helianthine. . . . . . . . . . Phenol. . . . . . . . . . . . . . 0 .I57 . I . .
Heated.
L -
Colors or Hel. decomposes. Melts. 211°
0.20 0.05
I94O
198' 224'
146'
155'
0.11 0.IO
....
0.50 0.40
167 a 219'
0.20
0.09 0.07
Color whena heated, 130 .
helianthine
orange helianthine helianthine
211°
209 O 165' 180' 223'
brown black helianthine orange-brown helianthine
0.23
158' 194' 2.54'
0 .IO
50.00
.... 0.09 0.60
157'
0 .I 2
202 O
0.20
203'
....
234O
0 .I2
200O
............ helianthine brown helianthine
Special Observations. The contents of water in the above salts were determined by heating a t 100-130' for one or more hours; heating to constant weight was not often possible, for the reason that the salts undergo secondary decomposiI.
1580
W. A . JACOSS, &I. .H€:JDEI,SERGER AND IDA P. ROLF.
tion. This was especially marked in the u s e of the barium salt; tests for methyl alcohol and for dimethylamine gave negative results. 2. The solubility of pure helianthine in water is 0.02 g. per liter; the solubilities of all 01 its salts are greater than this. This can indicate that its salts are not completely hydrolyzed. Since solutions of its salts are partially or largely hydrolyzed, as shown in previous studies,' and these colors are not parallel to these solubilities, it may be concluded that the chromoisomerizations of helianthine are largely dependent upon the stabilities of the salts toward mater. 3. KO obvious conclusion can as yet be drawn from studies of the melting points of helianthine salts. The formation of salts by other indicators will be studied. S ~ A T T LWASH E,
THE ROCKEFELLER INSTITUTE MEDICALRESEARCH.]
[CONTRIBUTION FROM THE LABORATORlES OF
FOR
ON NITRO- AND AMINOARYL ARSONIC ACIDS. BY WALTERA
MICHABLHRIDELBERGBR AND IDA P. ROLF Received July 9, 1918
JACOBS,
In the course of studies on the synthesis of organic arsenic compounds for therapeutic purposes it was found necessary to prepare a number of aminoaryl arsonic acids. It was therefore of importance to find methods which would furnish these substances in amounts sufficient for synthetic work. Of the methods available the application of the Bechamp synthesis, first used for the preparation of arsanilic acid, has rendered directly accessible only a limited number, mainly p-aminoaryl arsonic acids. Tn order to obtain a- and m-amino arsonic acids it has usually been necessary to employ indirect methods. The most useful of these involves the preparation of the corresponding nitro compound, which is then reduced to the desired amino acid. I n case the nitro acid is synthesized by direct nitration of an ary1 arsonic acid, only the m-nitro compound can be obtained. More general, however, is Bart's excellent methodZin which a diazo or isodiazo group is replaced by the arsonic acid residue. This reaction has greatly increased the availability of aromatic arsonic acids, many of which have been unobtainable by other means. Among the wide variety of examples given by Bart are enough to demonstrate the value of the method for the preparation of the nitro arsonic acids and his procedure was, in fact, used later in a few instances by otherss for the same purpose. In the present work we have found the method to be of exceptional THISJOURNAL, 39, 1373 (19171. See especially the potassium salt. Bart, D. R P. 250,264. TI R P. 266,944, 267,307; Bauer, Bev., 48, 1582 (1915).
