518 THE JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 9, No. 5

TABLEVI-Tiie EFFECTOF SULFURICACID TREATMENT ON THE AVAILABILITYOF THE NITROGENIN GARBAGETANKAOE FROM PENN.REDUCTION COMPANY PHILADELPHIA,PA. . SUM OF WATER- Weight of Sample WATER- INSOLUBLENITROGEN WATER- Containing 50 mg. INSOLUBLENITROGEN RENDEREDSOLUBLE Volume of PER CENT NITROG$N SOLUBLEWater-Insoluble N RENDEREDSOLUBLE BY BY ALK.KMnOc AND Sulfuric r NITROGEN for Alk. ALKALINEPERMANGANATE WATER-SOLUBLENITROGEN Acid Total as Watu- Water- Per cent KMnO4 Det’n Percentages in terms of Percentages in terms of cc. found Insoluble Soluble of Total Grams Water-Insol. N Total N Total N Water-Insol. N n 2.91 2.58 0.33 11.34 1.9370 22.60 20.03 31.37 33.94 16 2.82 2.43 0.39 13.83 2.0580 21 .oo 18.10 31.93 34.83 30 2.70 2.23 0.47 17.42 2.2420 21.20 17.52 34.94 38.62 40 2.48 1.90 0.58 23.39 2.6320 21.60 16.54 39.93 44.99 50 2.34 1.80 0.54 23.07 2.7780 20.60 18.74 41.81 43.67 60 2.30 1.64 0.66 28.70 3.0490 21.40 15.25 43.95 50.10 70.. 2.20 1.46 0.74 33.64 3.4250 20.80 13.80 47.44 54.44 80 2.30 1.48 0.82 35.65 3.3790 20.60 13.25 49.90 56.25 90 2.30 1.47 0.83 36.07 3.4010 20.60 13.15 49.32 56.67 100 2.10 1.34 0.76 36.18 3.7310 21.40 13.70 49.88 57.58 ment would be economically feasible would depend to some extent. It will be noted that it belongs to the on various conditions. In the preparation of mixed same family as rhubarb, as does also Polygonum fertilizer it might be possible to utilize the excess acid cuspidaturn’ Sieb. et Zucc., which is indigenous to by mixing with rock phosphate and thus reduce the China and Japan. The U. S. Pharmacopoeia, 8th cost of the treatment. Edition, recognized all species of Aloe, while the 9th Edition recognizes only Perryi Baker, vera Lanne and CONCLUSION ferox Miller. The U. S. Pharmacopoeia recognizes The examination of the various garbage tankages the species frangula and purshiana of Rhamnus under has revealed no important fact that shows that they the names of frangula and cascara sagrada; those are unsuited for fertilizer materia!. The position is species of Rheum which come from China and Thibet; not taken that it is possible to determine the value of the species of acutifolia and angustijolia of Cassia a fertilizer material definitely by present methods of under the commercial names of Alexandria and India chemical analysis, but from the examination the ex- senna. pectation would seem entirely justified that the proper A great deal of work has been done on the con- use of garbage tankage should give the usual results stituents of the emodin-bearing drugs, notably by obtainable from medium or low-grade fertilizers. Tschirch and his co-workers in Switzerland and by Garbage tankage offers a large supply of nitrogen. Power and his co-workers in England. Relerence At the present time ever-increasing amounts of such to the more important work prior to 1911 may be ammoniates as cottonseed meal and high-grade tank- found in “Die Pflanzenstoffe” (Wehmer). The age are being utilized for feeding purposes rather than principal constituents of Aloes as given by Wehmer for fertilizer and there is a growing scarcity of high- are aloin, barbaloin, isobarbaloin, emodin, and aloe- grade nitrogen carriers.’ In view of these facts, the resin. wider use of the low-grade materials becomes increas- The constituents of Cascara are best given by H. A. ingly desirable. The intelligent use of garbage tank- D. Jowettz and summarized as follows: age will make available the not inconsiderable nitro- (‘I-In addition to emodin, the presence of which in gen which it is able to supply to the fertilizer trade the bark was fully confirmed, a small amount of a sub- and at the same time will tend to result in a larger stance isomeric with emodin, melting at 183’ C. was conservation of the garbage of the cities with in- found. Glucose also occurs in the bark. creased benefit to them. “2-NO evidence whatever could be obtained of the BUREAUOF SOILS existence of chrysophanic acid or chrysarobin in the U. s. DEPARTMENTOF AORICULTURE WASHINWCONv D. c. bark, or of glucosides yielding on hydrolysis emodin, chrysophanic acid or rhamnetin. ‘(3-It was impossible to isolate a pure substance THE IDENTIFICATIoN DRUGS corresponding to either cascarin or purshianin. By W.OF S. HUEBARD Received January 29, 1917 “4-Attempts to obtain the bitter principle or Emodin and emodin-like compounds are found in derivatives of it in crystalline form were unsuccessful. the various species of Aloe, family Liliaceae; various “5-” difference be Observed between the species of Rheum, family Polygonaceae; various species character of the fresh (1 Year old) and of the so-ca11ed bark years of Cassia,family Leguminosae, to which belongs senna; (3 Xanthoxylum tingoassuiba St. Hil., family Rytaceae; “6-The examination of Rhamnus purshianus D. C., various species of Rhamnus, family Rhamaceae, to and Rhamnus calijornicus Esch. gave identical results. which belong cascara and frangula; Rumex ecklonianus ((7-’ enzyme was which hy- Meissn; polygonum2 cuspidaturn Sieb. et zucc,family drolyzed amygdalin, but when administered in 1%- Polygonaceae; Xanthoxylum tingoassuiba St. Hil., a doses had no griping native of Brazil, is not very well known and apparently physiological experiments made for the not used. R~~~~ eck~onjanuss is an herb indigenous purpose of locating the active principle of the drug to South Africa where it has been used in medicine resulted in the following: Emodin is not the active principle, and exerts very little, if any, of the char- Report on the Fertilizer Industry, Federal Trade Commission, Aug., 1916. acteristic aperient action of cascara. The active * Die Pflanzenstoffe. Wehmer, Jena, 1911. 1 Perkin, J. Chem. Soc.. 67 (1895), 1084. * Tutin and Clewer. J. Chem. SOC.,97 (19101. I. 9 Report 47 (19041, of the Wellcome Research Laboratory. May, 191i THE JOl-R-VAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY 519 principle or principles producing the aperient action identify the drugs separately and in mixtures some of the drug are contained in the portion of the lead recognized tests have been combined, and others de- subacetate precipitate extracted by ethyl acetate, veloped as outlined below. It is necessary to try the which is soluble in water and in alcohol.” tests on authentic samples in order to become familiar The constituents of rhubarb are given by F. Tutin‘ with the colors produced by the individual substances and H. W. B. Clewer. In their paper a very good and by different combinations. The procedure indi- review of the literature is given and a number of points cated has been followed with success by various analysts are elucidated. The main constituents isolated were : in the Bureau of Chemistry during the past year and a Cinnamic acid, 0.01 per cent; gallic acid, 2.2 per cent; half. After some experience the analyst should have rhein, 0.I 2 per cent; emodin, 0.78 per cent; aloe-emodin, little difficulty in the identification of aloes, cascara, 0.16 per cent; emodin monomethyl ether, 0.22 per rhubarb, and senna. Frangula responds to the same cent; chrysophanic acid, 0.49 per cent; and rheinolic tests as cascara. acid (an anthraquinone derivative) ; in addition a PREPARATION OF SAMPLE mixture of glucosides (2.0 per cent) of rhein, emodin, aloe-emodin, emodin monomethyl ether, and chryso- In the case of liquids evaporate about IO cc. to a pasty consistency in a porcelain dish, acidulate with phanic acid; an amorphous, non-glucosidic resin, 10.4 per cent. Of the anthraquinone derivatives only aloe hydrochloric or sulfuric acid, and extract the contents emodin and chrysophanic acid have any purgative of the dish several times with ether, stirring with a action, the mixture of glucosides being inert. The glass rod and pouring off the ether into a test tube. chief purgative principle is the non-glucosidic resin. With pills or other solid material it is necessary only The constituents of senna leaves are given by F. to powder, acidulate and extract with ether as de- Tutk2 A very good review of the literature is given scribed. and a number of points are elucidated. Tinnevelly BORNTRAGER REACTION’ leaves were found to contain salicylic acid, rhein, To a portion of the ether extract is added ammonia kaempferol, aloe-emodin, kaempferin, and a mixture water or dilute alkali. If emodin or other anthra- of the glucosides of rhein and aloe-emodin. Senna quinone compounds are present a red color develops leaves from Lima and Peru were found to contain all in the water layer. these compounds and, in addition, isorhamnetin and a Phenolphthalein also gives this reaction, but if some glucoside of isorhamnetin. Alexandria senna yielded of the ether solution is evaporated to dryness and rhein, aloe-emodin, kaemferol, and isorhamnetin, also sodium or potassium hydroxide solution (5-10 per cent) the glucosides of these. The glucosides were found added, the color given by phenolphthalein disappears to be more abundant. Attention is called to the fact after a short time (an hour or two), while the color that “Cathartic acid” of Dragendorff has been for of the anthraquinone compounds is permanent. If some time recognized as an indefinite mixture of sub- phenolphthalein and anthraquinone compounds are stances. Quite contrary to what has been the usual both present the method of Warren2 should be used for belief, and contrary to the statement in most books separating them. It is as follows: dealing with the subject, no chrysophanic acid was “The preparation in the form of a syrup is diluted found in senna. with water, faintly acidified and filtered to remove While a great deal of work has been done on the most of the phenolphthalein. The filtrate is neutralized constituents of aloes, cascara, rhubarb and senna, with ammonia water, evaporated to a very thick syrup comparatively little has been done on the identifica- which is extracted while warm with acetone, and tion of them when in medicinal preparations or ad- rendered slightly acid with hydrochloric acid. The mixtures. E. M. Bailey,s reporting some results ob- extraction is made by stirring with successive portions tained in an effort to find some color reaction which of the solvent3 and decanting from the residue. The would serve to differentiate between these cathartics, acetone fractions are united, evaporated to dryness states: “While experiments have thus far fallen short on the water bath, the residue twice moistened with of success in this respect, they have, nevertheless, alcohol and the alcohol evaporated in order to remove led to some interesting differences among the oxy- the last traces of acetone.4 The residue is taken up methylanthraquinones themselves.” A separation is in diluted sodium hydroxide solution, filtered, and a made of the anthraquinone compounds by means of slight excess of iodine test solution added, followed ammonium carbonate, sodium carbonate and sodium after a few minutes by the addition of a slight excess hydroxide, the method employed by Tschirch, the of hydrochloric acid. The container is cooled below Wellcome Research Laboratories and others. 15’ C. for an hour and the contents filtered. The The greater part of the work along these lines has phenolphthalein is thus precipitated as tetraiodo- been on the chemical identification of aloes and phthalein, a substance which is very insoluble in water. differentiation of the species. The solution is then treated with a slight excess of A majority of the nostrums on the market contain sodium sulfite, to remove free iodine, and shaken with one or more of the emodin-bearing drugs. In order to chloroform. The chloroform is evaporated to dryness and the residue treated with a dilute solution of soditim J. Chem. Soc., 99 (1911), 946 or Report 126 (1911) Wellcome Re- search Laboratory. 1 Z. anal. Chem., 19 (1880). 165. E J. Chem. Soc.. 108 (1913). 2006, or Report 117 (1913), Wellcome Re- 2 Am. J. Pharm., 86 (1914). 444. search Laboratories. * The author prefers ether instead of acetone. *Am. J. Pharm. 87 (1915), 145. 4 If ether is used these evaporations are unnecessary. 520 THE JOURlVdL OF INDrSTRIAL AND ENGINEERING CHEMISTRY Vol. 9, NO. 5 hydroxide which develops a red color in the presence of It is said that aloes are sometimes found which do anthraquinone compounds.” not contain emodin’ but so far as the author can Another method, described by E. VI. Bailey,l is of ascertain this is very rare. It has no bearing on the about equal value for the elimination of phenol- borax test. If emodin is absent it will of course fail phthalein and also eliminates curcumin (the coloring to give the Borntrager reaction. substance of Curcuma longa) and haematoxylin. The Other tests for aloes have been proposed: Klunge’s solution is treated with zinc dust in the presence of reaction2 by the addition of copper sulfate gives a 2j per cent sodium hydroxide and the anthranol is yellow color and after addition of salt and alcohol a oxidized back to chrysophanic acid by means of red color develops. This is not distinctive for aloes. hydrogen peroxide. In a later paper2 Bailey states Kremel’s Chrysaminic Acid TestS by the trans- that, “The reaction utilized to identify, chrysophanic formation of aloin to chrysaminic acid by evaporation acid in the presence of phenolphthalein serves also as with nitric acid and addition of ammonia or other a test for oxymethylanthraquinones, generally, and is alkalies. This reaction is also given by substances much more specific for this group than the Born- other than aloes. trager reaction.” The Hirschsohn’s test4 is applied after purification The procedure is, however, so complicated that it with basic lead acetate. To IO cc. of the filtrate add would rarely be used in place of the Borntrager re- a few drops of copper sulfate solution and hydrogen action. Since all the emodin-bearing drugs discussed peroxide and warm, but not to boiling. In the presence in this paper contain oxymethylanthraquinones, the of aloes a deep red color appears, which increases in reaction described does not help to distinguish between intensity on standing. This is not distinctive for the individual emodin-bearing drugs. aloes. BORAX TEST3 SIossler5 describes a method to avoid the precipita- After the presence of an anthraquinone compound tion of aloin with foreign oxyanthraquinones, etc., by is shown by the Borntrager test and phenolphthalein lead acetate whereby the Hirschsohne and borax test is shown to be absent or is eliminated by one of the for aloes are more distinctive. It is claimed that methods given, the borax test is applied. To a portion 0.2 g. of aloes can be detected in a mixture containing of the ether extract in a test tube is added an equal I j g. of rhubarb, frangula or cascara. The method is amount of saturated borax s~lution.~In the presence rather tedious and must be followed very carefully to of aloes a green fluorescence develops in the aqueous obtain satisfactory results. layer. It sometimes requires half an hour for the RHUBARB fluorescence to ‘become noticeable. With the borax An aqueous solution of chlorinated lime is added solution rhubarb shows an old rose color, cascara a to a portion of the ether extract and in the presence of brown and senna sometimes a light’brown but usually rhubarb a red color appears in the water solution. no color. With a little experience there is no diffi- Sometimes only a red ring forms at the point of contact culty in distinguishing between cascara and senna. of water and ether, and if large quantities of rhubarb From this borax test an idea is obtained of the particular are present a red precipitate is formed between the drug present, and confirmatory tests are then ap- ether and water. Chlorine water will not react. Both plied. calcium chloride and calcium oxide give a pink to red ALOES color with aloes, cascara and senna, as well as with The borax test is carried out as described in the rhubarb. If a saturated aqueous solution of ferric or U.S. Pharmacopoeia, 9th Ed. (1916), p. 37. The test is ferrous sulfate is used instead of the solution of best conducted in a IOO cc. graduated cylinder and chlorinated lime, the water layer assumes a blue color, allowed to stand at least an hour before deciding that sometimes quite faint, but evident when viewed with there is no fluorescence. One might be led to be- a white background. Aloes, cascara and senna do not lieve from the pharmacopoeia that this test iq dis- respond to this test. At the present time the causes tinctive for the species recognized, but as a matter of of these two reactions are not known and the questions fact it applies to all species of aloes. are being studied. It is necessary to have both of Aloin5 gives the fluorescence test of aloes either these tests positive before reporting rhubarb, for directly or when shaken out with ether. It does not samples of senna have been found on two occasions give the Borntrager reaction, but if ammonia or other which gave the test with chlorinated lime. St. John’ alkali is added directly to the aloin a red color de- has found that Acer spicatum gives the test with the velops. It is found that in carrying out the Born- iron salt. There has been recently imported into this trager reaction by addition of ammonia directly to the country, previous to the European war, a preparation ether a fluorescence develops after standing a short time. of I ,g-dioxyanthraquinone, called “Istizin,” used for 1 THISJOURNAL, 6 (1914), 320. the same general purpose as aloes, cascara, rhu- 2 Am. J. Pharm.. 87 (19151, 153. barb, and senna. It gives the Borntrager reaction 8 Pharm. Weekblad, 86, Maart, 1892, L. Schouteten. The author claims the test to be sensitive one part in ten thousand. In searching for 1 H. Herissey, J. Pharm. Chim.. 6 (1912), 393. thk reference, the qame has been found spelled three different ways, and in 2 Through Pharm. Post, 46 (1913), 313 no place has the correct reference been given to the original. In one case 8 Pharm. Post, 1895, 421. [Jahrber. der Pharm., 21 (1892). 1121, the reference gives thecorrect publica- 4 Pharm. Zentralhalle, 1901, 64. tion but the wrong year. 6 Pharm. Post. 46 (1913), 313. 4 The original test was for an aqueous solution of aloes. * LOC. Cil. U. S. Pharmacopoein, 9th Ed., 1916, 38. 7 Am. Pharm. Jour., January, 1917. hlay, 1917 THE JO17RAVALOF I,VDCSTRIdL A iVD E NGI -VE E RI NG C H E MIS T R Y j21 and the reaction with a solution of chlorinated lime, Senna is the most difficult to detect and is identified but does not give the test with the iron salt or borax by its failure to respond to any except the Born- solution. trager reaction. It is sometimes difficult to get senna ALOES AXD RHUBARB to respond even to the Borntrager reaction and this is When these substances are present in about equal no doubt due to the fact that glucosides of the anthra- amounts, or rhubarb in excess, it is Well to extract the quinone compounds are present in greater quantity acidified material with ether until practically no more than the compounds themselves. Senna cannot be yellow color is removed. The residue is then ex- identified in combination with any of the other drugs. tracted with hot water and tested according to the DEPARTMENTOF AGRICULTURE directions given in the U. S. Pharmacopoeia.’ If BUREAUOF CHEMISTRY, WASHINGTON the aloes is in excess, rhubarb does not interfere. THE DETERMINATION OF AND WATER IN CASCARA AND ALOES ALCOHOL ETHER FOR ANAESTHESIA The cascara solution sometimes gives a fluorescence By R. L. PERKINS which need not be confounded with aloes since the Received December 29, 1916 fluorescence of the former has a brown color; neither The Pharmacopoeia (V. S. P. IX, p. 32) describes need it be confused with a mixture of rhubarb and ether for anaesthesia as containing between 2.j and aloes, for the presence of rhubarb produces a reddish 4.j per cent of alcohol and a little water. No method color and is easily identified by the special tests already is given for determiping either of these substances described. If, however, aloes and cascara are both and there has been much uncertainty in the past as present, the fluorescence and brown color will both to the amounts of them present in anaesthetic ether. appear, in which case it is best to carry out the test Quite recently hlallinckrodt and Alt‘ have pub- according to the directions given in the U. S. Phar- lished a method in which the water is determined by macopoeia, 9th Edition,’ and carry the dilution to absorbing it with potassium carbonate and weighing joo cc. in a cylindrical graduate, at which concentra- the latter and the alcohol is determined in the dehy- tion the fluorescence of aloes will be very prominent drated mixture by specific gravity. and that of cascara will have disappeared. Prepara- This method appears to give satisfactory results tions containing “cascarin” may be identified as but it seemed to the writer simpler to determine water cascara, for it has been shown that “cascarin”* is not by the specific gravity of the original mixture. a definite chemical compound and contains the anthra- Regnauld and Adrian2 suggested this method in quinone compounds as well as the active constituents. 1864. They worked out a table of densities of ether- The colors produced by an aqueous solution of the alcohol-water mixtures. By means of this table, following chemicals on the ether extractions of these alcohol was determined from the specific gravity of drugs were found to be as follows: the sample after dehydration with potassium carbonate. AMMONIUM THIOCYANATE Water was then determined from the specific gravity Senna-yellow to brownish color in water layer. Rhubarb-green to yellowish color in water layer. of the original mixture. Their results were expressed Cascara-brownish to rose-red color in water layer. only to the third decimal place. Since it requires Aloes-red in ether and brown in water layer. a change of about I per cent of alcohol or 0.2 per cent AMMONIUMMOLYBDATE of water to affect the third decimal place, the results Aloes and cascara-no color change. obtained by the use of their table would be crude at Rhubarb-mahogany-brown in water layer. Senna-very light brown to yellowish in water layer. best. So far as is known to the writer no better data have Ammonium sulfate, ammonium persulfate and am- since been published. The work described below monium oxalate give no color change. was, therefore, undertaken for the purpose of supply- URANIUMACETATE ing more satisfactory figures. Aloes, cascara and senna-n> color change. Rhubarb-reddish mahogany color in water layer SPECIFIC GRAVITIES OF MIXTURES OF ETHER, ALCOHOL SUMMARY AND WATER Aloes can be identified by the fluorescence with Pure ether was prepared as follows: Anaesthetic borax solution no matter what combination of emodin- ether was shaken out three times with water and twice bearing drugs may be present. with alkaline permanganate solution. It was then Rhubarb can be identified by obtaining a positive dried several times over calcium chloride, and distilled. reaction with both chlorinated lime and iron sulfate The specific gravity was still high (about o.7100 un- solutions. No other substance, so far as known, will corrected), evidently due to incomplete dehydration. give both reactions. It was, therefore, allowed to stand over about IO Cascava is identified by the brown color imparted per cent of its weight of dried potassium carbonate to the water solution on the addition of borax solution for several days. The specific gravity was now 0.70968 to the ether extract provided the two tests for rhubarb uncorrected or, corrected to vacuum and 2 j O/z j O are negative. Cascara can be identified in any com- on the hydrogen scale, 0.70993. This compares very bination of the emodin-bearing drugs if rhubarb is favorably with the absolute ether obtained by Mallinck- absent. rodt and Alt and others. 1 LOG.Lit. THISJOURNAL, 8 (1916). 807. H. A. D. Jowett, Report 47 (19041, Wellcome Research Laboratories. * J. pharm. chrm , 45 (1864), 193.