[COMMUNICA!

CION

NO. 815

FROM THE

LABORATORIES] KODAERESEARCH

THE IDENTIFICATION OF AROMATIC SULFONIC ACIDS CONTAINING AN AMINO GROUP

C. F. H. ALLEN
AND

G. F. FRAME

Received August 8, 1941

Aromatic sulfonic acids are readily identified in most schemes of qualitative organic analysis (1) by formation of the sulfonamide. A less familiar method is the production of salts between the acids and amines, or amine derivatives (2-1 1). Where applicable, this latter procedure gives results in a much shorter time. Neither of these means of identification is applicable to sulfonic acids when there is an amino group present.' Inner salt formation prevents the use of the second procedure, and the sensitivity of the amino group to phosphorus pentachloride makes impossible the application of the first method. However, it has been found that when many aromatic sulfonic acids containing one amino group are diazotized and the NH2 replaced by C1 by means of the Sandmeyer reaction, the resulting chlorosulfonic acid is readily converted into a crystalline sulfonamide with a good melting point. Though several steps are involved, the yields are good in each, and one gram of the amino sulfonic acid gives sufficient chlorosulfonamide for identification. In Table I are collected the melting points of the chlorosulfonamides derived from the common amino sulfonic acids. The method is applicable to amino mono- and di-sulfonic acids in the benzene series and to monosulfonic acids in the naphthalene series. In the case of disulfonic acids in the latter series, the steps are satisfactory only to the formation of the disulfonyl chloride, owing to the very high 3 5 0 ' ) of the disulfonamides. While the disulfonchlorides melting points ( are all solids with convenient melting points, in general they do not crystallize well, and are unsuited for qualitative organic analysis. Fortunately, the disulfonanilides have good melting points and are easily secured; in Table I1 are recorded the properties of the derivatives of the common amino polysulfonic acids.
1 Substances of uncertain constitution resulting from the use of S-beneylthiuronium chloride together with their decomposition points have been described recently (11). 15

16

C. F. H. ALLEN AND G. F. FRAME

2-Naphthylamine-3,6-disulfonicacid yields a chloronaphthalene disulfonchloride (m.p. 165') that crystallizes readily, so this derivative also serves for purposes of identification.
TABLE I MELTING POINTS OF AROMATIC CHLOROSULFONAMIDES
AMINOSULFONIC ACID USED M.P. (%)a

Orthanilic (12). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Metanilic (13). . . . . . . . . . . . . . . . . . . . Sulfanilic (14). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-Aminotoluene-2-sulfonic (15). . . . .................... 4-Aminotoluene-3-sulfonic (16). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-Aminotoluene-4-sulfonic (17) ..................... 2-Aminotoluene-5-sulfonic. . . . 4-Nitroaniline-2-sulfonic (20) ..................... 4-Nitroaniline-3-sulfonic (21). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Aniline-2,4-disulfonic (22). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A4niline-2,5-di~ulfonic (19). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-Aminonaphthalene-4-sulfonic (23)b.. . . . . . . . . . . . . . . . . . . . . . . .

188 148 144 145 156 135 128 (18), 131 (19) 185 158 217 229 187

2-Aminonaphthalene-1-sulfonic(29) . 2-Aminonaphthalene-5-sulfonic (26) . . . . . . . . . . . . . . . . . . . . . . . . . 2-Aminonaphthalene-6-sulfonic(30) ................... 2-Aminonaphthalene-7-sulfonic (30). . . . . . . . . . . . . . . . . . . . . . . . .

153 214 184 176

Melting points are uncorrected. 1-aminonaphthalene-2-sulfonic acid forms a 1-chloronaphthalene-2-sulfonamide which is reported as having no melting point up to 250" (24).
5

* The

TABLE I1

PROPERTIES OF CHLORONAPHTHALENE POLYSULFONANILIDES

NAPHTBYLAMINE SULFONIC ACID USED SOLVENT

l-Naphthylamine-4,8-disulfonic acid.. . . . . . . . . . . 2-Naphthylamine-3,6-disulfonic acid. . . . . . . . . . . 2-Naphthylamine-4,8-disulfonic acid. . . . . . . . . . . 2-~aphthylamine-5,7-disulfonic acid. . . . . . . . . . . 2-Kaphthylamine-6,8-disulfonic acid. . . . . . . . . . . l-Kaphthylamine-3,6,8-trisulfonic acidb... . . . . .

Benzene Benzene-ligroin Chlorobenzene Dil. acetic acid Chlorobenzene Chlorobenzene

233 185 235 206 192 249

5.8 5.9 5.9 6.1, 5.8 5.8 6.5, 6.8

IDENTIFICATION OF AROMATIC SULFONIC ACIDS EXPERIMENTAL

17

Most of the aromatic amino sulfonic acids are encountered in varying degrees of purity as intermediates for the manufacture of commercial dyes, and require more or less purification as a preliminary operation t o their identification. Usually, recrystallization from water in the presence of decolorizing carbon is sufficient; the addition of a little mineral acid is often advantageous. For example, 50 g. of acid was dissolved i n 250 cc. of a technical grade of 2-naphthylamine-4,8-disulfonic boiling water containing 2 g. of Norit and filtered. On cooling, 25.8 g. of the amino acid separated in the form of white needles. Qualitative procedure; A , for sulfonamides. It is advisable to start with 1.5-2 g. of recrystallized amino sulfonic acid in order t o have an ample amount of derivative. Usually i t is advantageous first t o dissolve the acid in sodium carbonate solution, and then to acidify and diazotize. The indirect procedure does not seem to give as good will serve as results. Details for the preparation of 4-chlorotoluene-3-sulfonamide an illustration. One and four-tenths grams of 4-aminotoluene-3-sulfonic acid (previously recrystallized from water) is dissolved in 10 cc. of water containing 0.41 g. of sodium carbonate. The solution is diazotized by adding 1 . 9 cc. of concentrated hydrochloric acid and then, quickly, 4.4 cc. of sodium nitrite solution (containing 120 g. of sodium nitrite per l.), the temperature being maintained at 10-15' by the addition of ice. Meanwhile, a cuprous chloride solution is prepared (32) from 2.16 g. of copper sulfate, 0.56 g. of sodium chloride, 0.46 g. of sodium bisulfite, and 0.33 g. of sodium hydroxide; this requires about ten minutes. The cuprous chloride is dissolved i n 10 cc. of concentrated hydrochloric acid and cooled in ice to 5". At this temperature the diazonium solution is added fairly rapidly while stirring. The temperature is allowed to rise slowly to room temperature and stirring is continued for one hour, after which the solution is heated t o 60-70" for thirty minutes on the steam-bath. The copper is then precipitated by hydrogen sulfide, the resulting copper sulfide is filtered, and the crude 4-chlorotoluene-3-sulfonicacid is obtained by evaporating the filtrate to dryness on the steam-bath. The crude acid is then mixed with double its weight of phosphorus pentachloride in a small beaker. When the vigorous reaction has ended, the beaker is heated in an oil-bath t o 130-140" for a short time t o expel the phosphorus oxychloride. After cooling, the chloride is washed by decantation with cold water, the resulting oil added to 45 cc. of concentrated ammonium hydroxide, and the solution evaporated t o dryness on the steam-bath. The crude sulfonamide remains as a residue and weighs 1.8 g. For purification i t is recrystallized, with the addition of Korit, from 85 cc. of boiling water. The 4-chlorotoluene-3-sulfonamide is obtained in the form of slender white needles which melt a t 155-156". Chlorobenzene-2,5-disulfonamide (I) and 2-chlorotoluene-5-sulfonamide (11) are new. Both crystallize as needles from water. Anal. I. (m.p. 229"). Calc'd for CeH7C1Ns04Sz: N, 10.4 Found: N, 10.4. 11. (m.p. 131"). Calc'd for C7H8C1Pi02S:N, 6.8. Found: N, 7.0. B , for sulfonanilides. The crude sulfonchloride (about 2 8.) secured as described is dissolved in 10 cc. of benzene, 2.5 g. of aniline is added, and the solution is refluxed for one hour. The solution is concentrated to half its volume and chilled. The resulting solid is filtered, washed with warm water, and recrystallized three times from chlorobenzene. The chloronaphthalene polysulfonanilides, the properties of which are given in Table 11, were secured by this procedure. They retain traces of the solvent used

18

C. F. H. ALLEN AND

a.

F. FRAME

for crystallization rather tenaciously, but this does not interfere with the determination of the melting point when done in the ordinary manner. When used for qualitative analysis of unknowns, the solubility i n benzene is first determined; if too soluble, ligroin (b.p. 9 0 1 2 0 ) is added. The insoluble derivatives are then handled with chlorobenzene and ligroin in a similar manner.
SUMMARY

A convenient method for the identification of amino sulfonic acids in the benzene and naphthalene series has been devised. It consists of replacement of the amino group by chlorine through the Sandmeyer reaction followed by a conversion of the sulfonic acid group to a sulfonamide or sulfonanilide. The procedure can be used in small quantities (1.5-2 g.) in qualitative organic analysis.
ROCHESTER, N . Y.
REFERENCES

(1) SHRINER AND FUSON, The Systematic Zdentijkation of Organic Compounds, 2nd Ed., p. 176-177, John Wiley & Sons, Inc., New York, ( 1 9 4 0 ) . ( 2 ) LYNCH, J.Ind. Eng. Chem., 14,964( 1 9 2 2 ) . AND SEWELL, J. Soc. Chem. Ind., 42,27T( 1 9 2 3 ) . ( 3 ) PERKIN ( 4 )FORSTER AND KEYWORTH, J . SOC. Chem. Ind., 43,165T, 299T ( 1 9 2 4 ) . (5) AMBLER AND WHERRY, J.Ind. Eng. Chem., 12,1085( 1 9 2 0 ) . (6) CHAMBERS AND SCHERER, Ind. Eng. Chem., 16,1272 ( 1 9 2 4 ) . ( 7 ) PERKIN AND COPE,J. Chem. SOC., 66,845( 1 8 9 4 ) . ( 8 ) DAVIDSON, J . Chem. Education,17,83( 1 9 4 0 ) . ( 9 ) AMBLER, J.Ind. Eng. Chem., 12,1081( 1 9 2 0 ) . ( 1 0 ) ERDMANN AND SUVERN, Ann..,276,297( 1 8 9 3 ) . (11) CHAMBERS AND WATT, J. Org. Chem., 6,3 7 6( 1 9 4 1 ) . ( 1 2 ) BAHLMANN, Ann., 186,325( 1 8 7 7 ) . ( 1 3 ) LIMPRICHT, Ann., 180,88 ( 1 8 7 6 ) ;PAAL, Ber., 34,2755 ( 1 9 0 1 ) . ( 1 4 ) OTTOAND BRUMER, Ann., 143,108 ( 1 8 6 7 ) ;GOSLICH, Ann., 180,1 0 6( 1 8 7 6 ) . (15) DEROODE, Am. Chem. J., 13,225 ( 1 8 9 1 ) . ( 1 6 ) WYNNE AND BRUCE, J. Chem. SOC., 73,760( 1 8 9 8 ) . ( 1 7 ) LIMPRICHT AND PAYSAN, Ann., 221,212( 1 8 8 3 ) . (18) WYNNE, J.Chem. Soc., 61,1041( 1 8 9 2 ) . ( 1 9 ) This paper. ( 2 0 ) CLAUS AND MANN, Ann., 266,91( 1 8 9 1 ) . (21) LAUBENHEIMER, Ber., 16,5 9 9( 1 8 8 2 ) . ( 2 2 ) OLIVIER,Rec. trav. chim., 37,307 ( 1 9 1 8 ) . ( 2 3 ) ARNELL, Ber., 17,Ref 48 ( 1 8 8 4 ) . (24) CLEVE, Ber., 24,3475 ( 1 8 9 1 ) . ( 2 5 ) CLEVE,Ber., 20,73 ( 1 8 8 7 ) . ( 2 6 ) CLEVE,Ber., 26,2481 ( 1 8 9 2 ) . (27) ARMSTRONGAND WYNNE, Chem. News 69, 1 8 9( 1 8 8 9 ) . ( 2 8 ) CLEVE, Ber., 23,963( 1 8 9 0 ) . ( 2 9 ) ARMSTRONG AND WYNNE, Chem. News 73,54( 1 8 9 6 ) . ( 3 0 ) FORSLING, Ber., 20,80 ( 1 8 8 7 ) . ( 3 1 ) FORSLING, Ber., 21,2803( 1 8 8 8 ) . ( 3 2 ) Org. Syntheses, Coll. Vol. I, 163 ( 1 9 3 2 ) .