1 
 
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A REVISION OF THE PROXIMATE COMPOSITION OF RHAMNUS 
 
 PURSHIANA 
 
 BY 
 
 FRED WARD ALWOOD 
 B. S. University of Illinois, 1920 
 
 THESIS 
 
 Submitted in Partial Fulfillment of the Requirements for the 
 
 Degree of 
 
 MASTER OF SCIENCE 
 IN CHEMISTRY 
 
 IN 
 
 THE GRADUATE SCHOOL 
 
 OF THE 
 
 UNIVERSITY OF ILLINOIS 
 
 1921 
 
UNIVERSITY OF ILLINOIS 
 
 THE GRADUATE SCHOOL 
 
 JUNE 4 192JL 
 
 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY 
 
 SUPERVISION BY FRED V/ARD AL^VOOD 
 
 C 
 
 ENTITLED . /I LEVI! 
 
 o: 
 
 PURSHIANA 
 
 BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR 
 
 Recommendation concurred in* 
 
 Committee 
 
 on 
 
 Final Examination* 
 
 
 *Required for doctor’s degree but not for master’s 
 

 
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ACKiroV/LaDGUdElHT 
 
 I wish to express my appreciation to Dr. 
 George D. Beal under whose direction and ad'vice 
 this work has "been carried out. The success and 
 results are due largely to his helpfulness and 
 suggestions given in carrying out the experimental 
 Y/ork of this paper. 
 
 J 
 
Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/details/revisionofproximOOalwo 
 
TABLil 0? GOITTailTS 
 
 Page 
 
 I. 
 
 IIIIHODUCIIOH 
 
 3 
 
 II. 
 
 EISTOHICAL 
 
 4 
 
 III. 
 
 EXPERILSETAL 
 
 8 
 
 
 A. Water Soluble l-iatter 
 
 12 
 
 
 B. Hot Water Extract 
 
 15 
 
 IV. 
 
 SUMiAHY 
 
 17 
 
 V. 
 
 BIBLIOGRAPHY 
 
 19 
 
3 
 
 llITRQDUCglOH 
 
 The work undertaken was a continuance of work done last 
 year hy the author. At that time more attention was given to 
 the insoluble resin and its products. The \7ater soluble matter 
 was also examined, but during evaporation of the solution it 
 caramelized, making identification of the sugars impossible. 
 
 From the results obtained it v/as concluded that a portion 
 at least of the anthraquinone derivatives are present as gluco- 
 sides, or in some other combined form. The work on the water 
 soluble matter was continued this year with the results which 
 follow in the experimental part of the investigation. 
 
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4 
 
 IiISTORIC.'lL 
 
 Since the latter part of the eighteenth century, there have 
 been described various naturally occurring dyestuffs which are 
 yellow in the free state and give red colors with alkalies. These 
 dyestuffs, as prepared, by early workers, were not chemical individ- 
 uals . 
 
 ( 1 ) 
 
 In 1858 De La Rue and Miller isolated pure emodin, and 
 in 1875 Schmidt (2) distilled aloes ?/ith zinc dust, obtaining 
 
 methyl anthracene. I'his was the first real evidence of the struc- 
 
 so 
 
 ture of these compounds, and remained until 1911, when Fischer and 
 Sapper (3), and Fischer, Falro and Gross were able to prove that 
 the hydrocarbon obtained from chrysophanic acid was B methyl an- 
 thracene . 
 
 Oesterle has shov;n (5) that emodin monomethyl ether is 
 usually associated with chrysophanic acid. It was due to his v;ork 
 (6) that chrysophanic acid, aloe emiodin and rhein v;ere shown to be 
 different stages in the oxidation of the same hydroxymethyl anthra- 
 quinone, while emodin is a tri-hydroxy-methyl anthraquinone . 
 
 The structure of aloe-emodin was nroved to be 
 
 o 
 
 This structure being proved, the structures of rhein and chryso- 
 phanic acid were established as follows:- 
 
 Ctti-OV\ 
 
 
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 ^ ah 
 
 
 
 0 
 

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5 
 
 the structural formula for emodin has not 
 heen established exactly, but a large amount of work has been done 
 by Jowett 1 Potter (7), Oesterle and Tisza (8), and by Oesterle, 
 and in 1915 ( 9 ) he came to the conclusion that the formula was:- 
 
 o 
 
 Dohme and Iilnglehardt (10) in 1898 stated that cascara does 
 not contain emodin as such, but a glucoside, yielding emodin on 
 hydrolysis. The glucoside v;as prefaced, by first extracting the 
 drug with chloroform to remove the fat, and then with 80/d alcohol. 
 The alcohol was distilled off and the residual extract taken up 
 with water and precipitated with lead acetate. The precipitate 
 was filtered off, stirred with hot water and hydrogen sulfide passed 
 in. The sulfides were filtered off and the solution evaporated. 
 
 This filtrate was treated with lead subacetate and the precipitate 
 decomposed with hydrogen sulfide. The filtrate from the sulfides 
 was evaporated, to dryness. A hard brovmish-red. substance v/as ob- 
 tained, which would only be crystallized with great difficulty. 
 
 They tried crystallizing in acetone and. ethyl acetate, but only ob- 
 tained a fev; dark red needles, melting at 237'^C. They stated that 
 it was not emodin, since it gave no purplish color with caustic 
 potash, and that it was a glucoside characteristic of the drug. 
 
 IIo proof of the purity of the crystals v/as given. It v/ould 
 be expected that any impurity present would modify the color re- 
 action. Prom this it would appear that the crystals were impure 
 emodin. llo proof is furnished of the glucosidal character of this 
 substance, and no tests for sugars were made previous to or after 
 
6 
 
 hydrolysis . 
 
 Thorpe and Hiller (11), and Beal and Gnnton ha-7e isolated 
 the glucoside frangulin from frangiila hark. It melts at 225° and 
 yields emodin and rhamnose on hydrolysis. They ha've also con- 
 firmed the formula of the glucosides as C2]_H2Q0g. On hydrolysis 
 and addition of one mole of water it yielded the products given 
 
 above. C 21 K 20 O 5 + ^ 2 '^ ^^15%0^5* 
 
 Beal and Gunton have also succeeded in preparing a rhamnoside 
 
 \> 
 
 of emodin hy the condensation of emodin with triacetyl from rhamnose 
 in the presence of alkali. The product, while impure, as shown hy 
 an indefinite melting point, behaved in a manner similar to frangu- 
 lin, and v;hen mixed with the supposed frangulin from frangula hark, 
 gave only a very slight lowering of the melting point of the mix- 
 ture . 
 
 Jowett and Potter made a detailed examination of the consti- 
 tution of the hark, special attention being directed to the results 
 already obtained hy other investigators. Where definite substances 
 were isolated, their purity was established, if possible, by chem- 
 ical methods. 
 
 The details of the experimental work are somewhat extended, 
 so only a summary of the results will be given. In addition to 
 emodin, an isomeric substance was isolated melting at 183°C, insol- 
 uble in ammonia, and its acetyl derivative melted at 168°C. Glu- 
 cose was proved to occur in the bark. 
 
 IIo evidence could be obtained of the existence of chryso- 
 phanic acid or chrysarobin in the bark, or of glucosides yielding 
 on hydrolysis emodin or chrysophanic acid. It was found that 
 
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 emodin, although insoluble in water, was soluble in the aqueous 
 extract of the bark and that it was extracted from such a solution 
 only slowly and with difficiilty by shaking with the imiscible sol- 
 vents. After treatment v/ith acids, the water soluble substances 
 were decomposed with formation of insolube resins and the emodin 
 vjas very readily extracted from such a mixture. 
 
 The bark contained about two per cent of fatty or waxy 
 material, which consisted of rhamnol arachidate, free arachidic 
 acid, and substances yielding on hydrolysis linolic acid, and myris- 
 tic acid. The name rhamnol has been assigned to the alcohol 
 melting at 135^-156°, which is combined with arachidic acid in cas- 
 cara. 
 

 
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 I^LXP^HIIvliilllTAL 
 
 The author's attention V7as nov/ directed towards the products 
 of the hydrolysis of rhamnus purshiana, the water soluble extract 
 being studied. When the bark was extracted in a percolator of the 
 ordinary type, the extract being concentrated by almost continuous 
 heating on the steam bath. An excellent yield of emodin was ob- 
 tained on extracting the dried resin with ether. When another, 
 and much larger, portion of the drug was extracted in the Lloyd 
 apparatus, in which the extract after having been rapidly concen- 
 trated was immediately chilled and kept cold, the yield of emodin 
 obtained from the resin by direct extraction was very much smaller. 
 
 It was thot that the difference in yield might be explained 
 by assuming the presence in the drug of an emodin containing gluco- 
 side, or other derivative, which was extracted in either instance 
 by the alcohol, but in the one case was broken do?;n by continuous 
 heating, yielding emodin which was easily extracted by ether. 
 
 The purpose of this investigation was to study the water 
 soluble extract and to attempt to establish the presence of a glu- 
 coside in the bark. 
 
 The material used for the examination was cascara bark, ob- 
 tained through Fuller, liorrison and Company, Wholesale Druggists, 
 of Chicago. The drug as received \vas in the form of quills, and 
 was ground to about number twenty powder in a Kance Mill. The drug 
 was moistened with alcohol, placed in the percolator of a Lloyd 
 ilxtraction Apparatus, covered with 95 /^> alcohol, and allowed to 
 macenate twenty-four hours, after which percolation was begun, and 
 continued until the dinig v;as completely exhausted. 
 

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 Concentration of the percolate uas carried out in the con- 
 centrator of the extraction apparatus, and was continuous during 
 the extraction. This concentrator is of a type making use of the 
 principle of surface e'vaporation, while the tendency is for the 
 heavier concentrate to he carried hy gravity to the lov;er portion 
 of the concentrator, thus removing it from the heated zone. The 
 extract is never exposed to heat for any period longer than one 
 minute, and is in addition rapidly cooled hy a water Jacket sur- 
 rounding the apparatus immediately helow the heater. This short 
 period of heating, coupled with rapid cooling, and the fact that 
 the extract is at no time brought in contact v/ith air, leads one to 
 believe that the extract, as thus obtained, must represent most 
 closely the actual nature of the extractives as they are present in 
 the tissues before extraction. 
 
 The extract obtained, representing the total alcohol soluble 
 material of the bark, was reddish brown in color, thick and syrupy. 
 This was mixed with enough alcohol to make a liquid having the vis- 
 cosity of a rather thin syrup, and sufficient "dT/o hydrochloric 
 acid added to give an actual acid concentration of one percent. The 
 flasK was placed on a steam bath, with a large funnel in the neck 
 of the flask to restrict circulation of air and loss of solvent, and 
 heated at such a rate that the alcohol simmered gently. The heat- 
 ing was continued for twenty-four hours, twice replenishing the al- 
 cohol lost by evaporation. At the end of that period the alcohol 
 remaining was distilled off until a thick viscious extract remained, 
 and this, while still warm, ?;as poured into a large volume of water 
 contained in a stone Jar, the water being vigorously stirred by 
 
10 
 
 means of a "blast of air. I'he precipitate obtained was a dense, 
 sticky mass, dark brown in color. This was filtered from an orange 
 yellow liquid, washed with water, and examined in 1919-EO, with 
 the following results. 
 
 The work of this year is carried on as a continuance of that 
 of last year, in which the hydrolysed resin was studied. The bark 
 was extracted with alcohol, the alcoholic extract hydrolyzed for 
 twenty-four hours with 1^ hydrochloric acid and poured into water. 
 The resin separating out was studied with the results which follow. 
 
 The precipitated resin, after being air-dried, was broken 
 into small fragments and placed in the inner tube of a large Soxh- 
 let extraction apparatus, where it was extracted with ether. The 
 resin during this extraction, possibly due to the presence of a 
 small amount of water, gradually cohered into a gummy mass, only 
 slightly permeable to the ether. When this stage was reached, the 
 resin -/as removed, dried and powdered again, then returned to the 
 extraction apparatus and the extraction with ether completed. The 
 resin, after the ether failed to dissolve more material, was dis- 
 solved in alcohol, hydrolyzed a second time with one percent hydro- 
 chloric acid, and precipitated and extracted with ether as before. 
 
 Since the anthraquinone derivatives present in the ether ex- 
 tract would differ in acidity by reason of variation in the number 
 of hydroxyl a«d carbonyl groups present, the ether solution was 
 shaken with solutions of progressively increasing basicity in order 
 to effect a partial separation. Accordingly the ether extract was 
 shaken in turn with solutions of ammonium carbonate, sodium carbon- 
 ate, and sodium hydroxide. 
 
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11 
 
 Ammonium Carlonate ij^xtract. 
 
 Shaking the ether solution vjith b^o ammonium carbonate 
 yielded a deep-red soliition. This extraction was repeated until 
 the carbonate solution became only slightly colored. The extracts 
 thus obtained were combined and acidified with hydrochloric acid, 
 forming a yellow precipitate, rather small in 'volume. The precipi- 
 tate thus obtained was recrystallized in part from alcohol and part- 
 ly from glacial acetic acid. The crystals were dried in air, and 
 melted at 248°C. uncorrected. From the melting point of the com- 
 pound this was found to be emodin. A mixture vjith an equal quan- 
 tity of emodin from other sources showed, no lowering of the melting 
 point . 
 
 An acetyl derivative was prepared by refluxing with acetic 
 anhydride and fused sodium acetate for one hour. On cooling the 
 solution, lemon yellow needles appeared. These were recrystallized 
 from glacial acetic acid, which after drying melted at 197*^, ■on- 
 corrected. This corresponds to the melting point and appearance 
 of triacetyl emodin as given in the literature, and as previously 
 obtained in this laboratory. 
 
 Sodium Carbonate iixtract . 
 
 The ether extract was then shaken out with b^o sodium carbon- 
 ate giving a deep-red solution. The extraction was repeated until 
 the sodium carbonate solution was only slightly colored. The ex- 
 tracts were combined and acidified with hydrochloric acid forming 
 an orange yellow precipitate, large in volume. The precipitate was 
 filtered and recrystallized from glacial acetic acid. The melting 
 

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12 
 
 point of this precipitate was 250-255*^0. This was shown to he 
 
 emodin by the method previously described. The triacetyl deriva- 
 
 0 
 
 tive prepared as before gave the yellow needles melting at 197 , 
 corresponding to triacetyl emodin. 
 
 taodium Hydroxide iilxtract. 
 
 The ether extract was shaken out with a 5^ solution of 
 sodium hydroxide until fresh portions of alkali added took on 
 only a slight color. The extracts were combined and acidified 
 with sulphuric acid, forming a dark brovm precipitate, very small 
 in volume. The precipitate was recrystallized from glacial acetic 
 acid. On attempting to determine the melting point of this 
 material, it darkened greatly and apparently decomposed, making it 
 impossible to observe the true melting point, The value lies 
 above 260OG. 
 
 The water soluble extract was treated and clai^ified for 
 examination last year, but on evaporating the solution caramelized 
 making any further identification impossible. It was due to this 
 fact that the following work was carried out. 
 
 The orange yellow filtrate, on standing in a closed con- 
 tainer, gradually deposited a lemon yellow precipitate. This was 
 filtered off, and the filtrate evaporated to a small volume under 
 a diminished pressure. 
 
 A. Water Soluble Hatter. 
 
 The filtrate from the hydrolyzed resin was filtered and 
 neutralized with barium carbonate, and filtered again. The fil- 
 trate was evaporated, under diminished pressure, to a small vol- 
 
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 ume and filtered. 
 
 The precipitates obtained were dried and united, and ex- 
 tracted in a Soxhlet apparatus with ethyl ether. The ether ex- 
 tract was shaken out siiccessively with 5^ solutions of ammonium 
 carbonate, sodium carbonate and sodium hydroxide. T'rom the 
 ammonium carbonate extract, after acidifying, only a small amount 
 of amorphous red resin was obtained. The sodium carbonate ex- 
 tract yielded emodin v/hich was recrystallized from glacial acetic 
 acid and was identical with the emodin described in the litera- 
 ture. The sodium hydroxide extract did not yield anything. 
 
 The filtrate was treated with lead acetate and a precipi- 
 tate, large in volume, was obtained. The filtrate was treated 
 with hydrogen sulphide to remove the excess lead, and the lead 
 sulphide filtered off. This solution was evaporated under 
 diminished pressure, passing carbon dioxide through the solution 
 during the evaporation. A portion of this solution, after re- 
 moval of the excess hydrogen sulphide, was tested to determine 
 the amount of sodium hydroxide necessary to neutralize the acid 
 present. Then, to the remainder of the solutions, a little less 
 than the amount needed to neutralize was added. This solution 
 was evaporated under diminished pressure, watching closely for 
 any signs of caramelization or formation of a product. A dark 
 brown resinous substance separated out during the evaporation. 
 
 This was filtered and dried, but no melting point could be 
 obtained. The filtrate was diluted with five volumes of absolute 
 alcohol, but no product crystallized out. This solution was 
 allowed to evaporate spontaneously, but nothing separated out ex- 
 

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14 
 
 cept more of the dark brown resin. A portion of the solution 
 was evaporated to dryness, and. some crystals separated out, but 
 on examination it was found to be sodium acetate. 
 
 The solution was tested for the presence of sugars by the 
 Molisch napthol test. A few drops of the solution were diluted 
 v;ith water, and to this was added napthol in chloroform solution; 
 concentrated sulfuric acid was poured down the side and a ring 
 was formed, which is characteristic of sugar solutions. 
 
 An attempt was then made to make an osazone by boiling 
 some of the solution with phenyl hydrazine hydrochloride and 
 sodium acetate, llo product of osazone could be obtained. A 
 brown precipitate separated out, but on trying to recrystallize 
 from 50/O alcohol nothing vms obtained. 
 
 A portion of the solution was then tested with I’ehling's 
 solution to see if there vjas any reduction. A precipitate of 
 red cupious oxide was obtained showing that sugars might possibly 
 be present. The reduction of the Fehling's solution, however, 
 may be due to some other constituent in the clarified solution. 
 
 The precipitate formed, on the standing of the water soluble 
 extract of the hydrolyzed resin, was dissolved out of the con- 
 tainers with 95% alcohol. The alcohol v/as then distilled off, 
 after extraction with ether, and recovered. The ether extract 
 was in turn shaken out with ammonium carbonate, sodium carbonate, 
 and sodium hydroxide. The ammonium carbonate and sodium hydroxide 
 solutions on acidifying yielded nothing. The sodium carbonate on 
 acidifying gave a brown precipitate. This precipitate was re- 
 crystallized from alcohol, most of the precipitate going into 
 
15 
 
 solution leaving a small amount of yellow substance, which did 
 not go into solution. This v;as filtered off, dried and. identified, 
 as emodin. 
 
 B. Hot Y/ater iixtract. 
 
 A hot water extraction of the ground hark was made and ex- 
 amined. The extract was dark brown in color and was evaporated 
 under dimiinished pressure to a small volume and clarified by add- 
 ing lead acetate and sodium phosphate, the phosphate being added 
 to remove the excess lead, thus doing away with the use of hydro- 
 gen sulphide and subsequent evaporation of the excess hydrogen 
 sulphide. This solution was evaporated, further to see if anything 
 ?/ould crystallize out, but only a dark brown substance came down. 
 The solution did not yield any precipitate on attempting to pre- 
 pare an osazone, but did reduce Fahling's solution forming the 
 characteristic red cuprous oxide. 
 
 The precipitate formed on standing of the extract, and the 
 precipitate from» the clarified solution was treated with acid and 
 hydrolyzed for twenty-four hours, but no test for sugars was ob- 
 tained on examination of the solution. 
 
 An attempt ?/as made to isolate the glucoside as Dohme and 
 Bnglehardt did in 1898. The solution was treated v/ith lead 
 acetate and filtered. This precipitate was taken up in hot water 
 and. hydrogen sulfide was passed in. The sulfides were filtered 
 off and the filtrate treated v;ith lead subacetate. The precipi- 
 tate was filtered off, taken up ?;ith hot water and hydrogen sul- 
 fide passed in to decompose the precipitate. The filtrate from 
 the sulfides was evaporated to dryness. A dark brownish-red sub- 
 
16 
 
 stance was obtained. An attempt to determine the melting point 
 was made, but could not be determined. 
 
17 
 
 ^UluivIARY 
 
 The follov/ing conclusions -were drawn from the preceding 
 
 year’s Vi/ork on the resin; 
 
 1. Powdered cascara was extracted under such conditions 
 
 that the extract coiilcl he concentrated with the minimum amount 
 of exposure of the concentrated material to heat, thus avoiding 
 decompositi on. 
 
 2« The extract so obtained was hydrolyzed in alcoholic 
 
 solution by means of one percent hydrochloric acid. 
 
 3. The resin precipitated from this solution showed the pre- 
 sence of a larger amount of emodin than the unhydrolyzed extract. 
 
 4. The presence of sugar in the water soluble extract from 
 the hydrolyzed resin was shovm, but the sugar was not identified. 
 
 5. Prom the results obtained it is concluded that a portion, 
 at least, of the anthraquinone derivatives are present as gluco- 
 sid.es, or in some other combined form.. 
 
 The following conclusions are dravm from the work of this 
 
 year on the v;ater soluble extract of the hydrolyzed resin. 
 
 1. The material separating out in the containers of the 
 v;ater soluble extract was examined and found to contain emiodin. 
 
 2. The filtrate from this material was neutralized, clari- 
 fied, and evaporated under diminished, pressure, but only a dark 
 brown resinous substance separated out. 
 
 3. The solution gave a test for sugars with Llolisch alpha 
 
 duct 
 
 naphthol reagent, but on testing for osazone formation, no pro- 
 was obtained. 
 
18 
 
 4. On lolling some of the solution with Fehling’s solution 
 a large precipitate of cuprous oxide was obtained, showing the 
 presence of sugars. 
 
 5. The hot water extract of the hark v/as clarified and test- 
 ed for sugars, hut no osazone could he obtained. 
 
 6. On attempting to isolate the glucoside, as Dohme and 
 iinglehardt did, only a dark hrovmish-red substance vms obtained. 
 It did not correspond with the substance which they obtained. 
 
 7. ITrom these results it is concluded that sugars are present 
 in the water soluble extract, but they could not be isolated. 
 
 (O 
 
 It does not seem probably that the glucoside can be isolated by 
 methods which have been used. 
 
19 . 
 
 BIBLIOGHAiPHY 
 
 (1) 
 
 Am. J. Pharm. 30 (1858) 442-447 
 
 
 (2) 
 
 Ber. 8 (1875) 1274 
 
 
 
 (3) 
 
 J. Prakt. Chem. 83 (1911) 
 
 203 
 
 
 (4) 
 
 Ibid. 83 (1911) 208 
 
 
 
 (5) 
 
 Aroh de Pharm. 243 (1905) 
 
 434; 248 
 
 (1910) 
 
 (6) 
 
 Proc. Amer. Pharm. Assoc. 
 
 45 (1897) 
 
 193 
 
 (7) 
 
 Trans. Chem. Soc. (1903) 
 
 1329 
 
 
 ( 8 ) 
 
 Arch de Pharm. 246 (1908) 
 
 114 
 
 
 ( 9 ) 
 
 Arch de Pharm. 252 (1915) 
 
 327 
 
 
 fic) 
 
 J. Amer. Pharm. Assoc. 45 
 
 (1897) 198-202 
 
 (11) 
 
 J. Chem. Soc. 61 (1891) 
 
 1. 
 
 
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