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