1418 WILLIAM M. DEHiY AKD SILAS F. SCOTT. the exception of petroleum ether, and very difficultly soluble in water. On heating with acids, benzaldehyde is split off. Calculatd for C,,H,,O,S,: C,70.36; H, j.j4; N,13.68. Pound : C,;o.o.+; H,j.52; S, 13.69. AUSTIN, TEXAS. [CONTRIBLTIOS FKOY TH13 UNIVERSITY OF \~ASHINGTON.] SOME CHARACTERISTIC COLOR REACTIONS PRODUCED BY SODIUM HYPOBROMITE. BY \VILI.IAM 31. DEHN AND SILAS F. SCOTT. Keceived July IO, 1goS. Since hippuric acid gave with sodium hypobromite a Yery charac- teristic color reaction,’ it was thought that other substances also would be affected characteristically by this reagent. This has proved to be the case and to such an extent that sodium hypobromite alone or combined with the use of ammonia can now be considered one of the most valuable reagents for detecting and distinguishing many phenolic and nitrogenous aromatic compounds. For the purpose of uniformity and of determining the limits of tests and comparing their respective delicacies, solutions of the various sub- stances were prepared in the following concentrations: I, I gram in IOO cc. of water; 11, in 1,000;111, in ~o,ooo;I\-, in 100,ooo; l’, in I,OOO,OOO. Alcohol was added when necessary to produce complete solution ; with bases, hydrochloric acid was used for the same purpose. With various concentrations of solutions quite difierent color effects may often be obtained and thus one sonietinies obtains results quite different from the results described in the literature. For this reason the concentrations of solution should always be indicated, also the quantity used, method of applying the reagent, quantity of reagent and the temperature. In the following experiments the reagent was applied, a drop at a time, to about j cc. of the solutions tested. \Yhen a series of colors are given they indicate the progressive effect either on standing or on adding more of the hypobromite solution. The following abbreviations are used to indicate the conditions and manner of applying tests. A. Treated with sodium hypobromite at ordinary temperature. A’. Treated with ammonia. then with sodium hypobromite at ordinary temperature. B. First heated to boiling, then treated with sodium hypobromite. B’. Treated with ammonia, then heated and finally treated with sodium hypobromite. Of course solutions should not be acid in reaction for then bromine is liberated from the hypobromite. Excess of ammonia should be avoided THISJOURNAL, this Number, Note I CHARACTERISTIC COLOR REACTIONS. 1419 for the reason that it destroys the hypobromite. Care should be ex- ercised that the hypobromite is added gradually for the reasons not only that often a series of colors may thereby be developed but that the possible destruction of color by an excess of hypobromite may be avoided. Con- ditions of experiments and concentrations of solutions yielding negative results are omitted in the following descriptions. When heat and the addition of ammonia give efiects that are the same as A, only the effects of the latter are described. Phenolic Compounds. Plzenol.’--B and BI-I, deep chrome-green; 11, same; 111, light sea- green. Ammonia is necessary and heat assists this color reaction. Pyrocaieclzzno1.-A, A’, B, BI-I, 11, bright green followed immediately by a deep brown. B, B’-111, pink-brown followed by amber-brown. Most sensitive with ammonia and heat. Color is changed to yellow by an excess of sodium hypobromite. lieso~cznol.--A-I, bromine-brown ; 11, amber-brown ; 111, straw-yellow, A’-I, deep brown-black; 11, deep amber-green. B-I, amber-brown; 11- amber-green ; 111, green-amber ; IV, straw-yellow. B’-I, deep brown. black; 11, deep amber-green; 111, green-amber; IV, faint pink. Color is intensified by the use of ammonia and heat; destroyed by an excess of sodium hypobromite and continued heat. Hydroquznol. - A-I, chrome-green, changing immediately through bromine-brown to deep brown-black ; 11, chrome-green to deep brown ; 111, transient light green. AI-I, deep brown; 11, same; 111, very tran- sient light green. B-ammonia itself imparts a golden-amber hue; I, dark brown; 11, deep amber; 111, light amber. Less sensitive with ammonia and heat; an excess of sodium hypobromite discharges the color, yielding odor resembling quinone. To Dzstzngcizsh the Dzhydmc Phenols.-To about 0.1per cent. solution of each add one drop of ammonia; hydroquinol gives a golden yellow color. Add 2-3 drops of sodium hypobromite; pyrocatechinol gives a dark brown, resorcinol gives a green, and hydroquinol gives a brown-red color. Pyrogallol.- -A-I, amber, brown-red, deep black-brown ; 11, amber, deep brown-red; 111, amber. AI-same as A but less sensitive. B- ammonia alone imparts an amber color; 1-111, same as above; IV, amber. Phlorogluczno1.-A-I, green-amber, green-brown, deep violet, deep violet-brown; 11, violet, red-brown, amber. A’-I, black-brown; 11, brown-red. B and BI-I, deep violet, deep brown-black; 11, deep violet; 111, violet. The violet color, best formed with ammonia in a warm solution, easily distinguishes phloroglucinol from the other phenols. A blue color with bleaching powder is described: Lex, Ber., 3, 458; Salkowski, Z. anal. Chem., TI, 316;Jsb. chem, 1873, 722. CHARACTERISTIC COLOR REACTIONS. 142I Vanillin, 3-rnethoxS-4-oxybenzaldehy~e. B’-I, 11, beautiful amber color. Arhzifi?z, -1-1, pink, amber; 11, same. B-I, deep nickel-green; 11, same. 13uqen01, 4-propenyl-2-methoxyphenol.A, A’, B, B’-I, 11, golden yellow, changing to deep brown. Oil oj Baj,, contains eugenol. 13’-I, clear deep red-brown; 11, brown- yellow. Xninionia alone gives a bright lemon-yellow. Oil oj pimento, contains eugenol. R’-I. red-amber, brown, deep red- brown; 11, red-amber, brown, amber. .Ammonia alone gives a bright lemon - yellow. Scores of other fixed and volatile oils, tested as described above, failed to give characteristic color tests. Homogeneous aromatic oils like safrol, apiol and anethol failed to give the color tests even after boiling for some time with concentrated alkalis. Under these conditions oil of winter- green gave the same green color as salicylic acid. CI’ullic Acid. -&I, pink, amber, brown, black-brown; 11, pink, pink- amber, grass-green, amber-green, brown, amber; 111, pink, brown, amber. alone give first a pink, then a grass-green and finally a brown color, but the action is greatly quickened and intensified by means of sodium hypobromite. Y’unnic Acid.--X-I, 11, pink, amber, brown, deep brown; 111, pink, pink-amber, amber; IV, pink. Alkalis alone give first a pink, then a brown color: here as with gallic acid, owing to the oxidizing power of the h>-pobromite,the action is greatly quickened and intensified. Aromatic Nitrogen Compounds. A?zilinc.--h---I, orange-red, deep red-brown ; 11, smoky amber, deep orange; 111, amber, dirty orange; I\-, light yellow. A’-I, orange, deep brown; 11, orange, deep brown; 111, amber. IVith A’-I solutions, odor of phenylisocyanide. 0-1’0121iil‘iize.---X-I, brick-red, violet, purple, purple-black, deep brown- black; 11, brown-red or orange-red; 111, red-amber; IV, light straw- yellow. .l’-I, violet, purple, purple-black ; 11: >-ellow, pink-amber, brown-red ; 111, golden yellow. Ii’ith .\’-I scjlutions, odor of phenyl- isocyanide. fi-Toluidz‘ne.-A-I, pink, rose-red, red-brown ; 11, pink, dirty yellow. A’-I, violet, dark brown; 11, pink-amber, golden brown. These two toluidines and aniline are easily distinguished by the orange color with aniline and by the changes of color and deeper colors of 0- toluidine. p-Phelz!tlcizetiiuiiI?‘?2e.-*1-1, bright blue-green, deep purple, black- purple, brown-black : 11, deep grass-green, deep purple, dirty brown; 111, grass-green, amber-brown, 17iolet purple, curdy white precipitate ; 1422 WILLIAM M. DEHN AND SILAS F. SCOTT. IY, bright amber. A’-I, dark blood-red, purple, brown-black; 11, deep brown-red; 111, amber. B’-I, 11, deep purple, brown; 111, brown, amber. Very characteristic color effects. 11z-Sitranil2‘nc,.--X-I, yellow, dirty brown; 11, ochre-yellow; 111, light yellow; -l’-I, red-brown; 11, dirty brown; 111, light yellow. P-.CdSaw’lic Acid-B’-I, deep red-brown ; TI, amber; 111, light yellow. Beizzu~riid( .-A’-I, 11, yellow. deep brown, brow-black, precipitate; 111, amber yellow. The color is not easily discharged by an excess of hypobromite. -In intense odor of phenylisocyanide is given off. I-’hoz!,lz~rcti2clnt‘.-=\’-I, brown or brown-red color, odor of phenyl- isocyanide; 11, cloudy yellow. W-1) orange, brown. Pi?cn ylh tlyazinc.-A-I ~ I I ! dirty orange, .4 1i1nionol, ammonia-phenylacetarnide. B’-Ij yellow-red colored pre- cipitate; 11, amber. Fatty amides and aniines fail to yield color efiects with sodium hypo- bromite, in fact no aliphatic compound responds to this reagent. It is specifically an arcmat,ic test reagent. Alkaloids. Some forty of the most common alkaloids and glucosides were tested with sodium hypobromite ; onl!. the following ones gave definite color reactions. ,loiphzize.--A’, B’-I, deep amber-brown; 11, amber; 111, light yellow. The test is best made with the use of ammonia; the color is discharged by an excess of hypobromite. Codciw uizd Uioriiize gave the same as morphine, only less sensitive. Apo)~zorplzin~‘.-,?L-I, deep brown, deep chrome-green ; 11, pink-amber, deep browii, deep chrome-green, lighter green, amber: 111, light pink, light yellow. This is a very characteristic reaction, particularly in solu- tion 11. PIz?,sosfij71iziizc 01’ E.seyiw.’-:l-I, light red; 11, pink. A’-I, deep blood-red; 11, bright bichromate-red; 111, rose-pink. Alkalis give a red color but the hypobromite with heat deeply intensifies the red.