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Investigation of the product formed in the reaction of quinoline hydrocholoride with zinc dust. Dong, Gordon 1956

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INVESTIGATION OF THE PRODUCT FORMED IN THE REACTION OF QUINOLINE HYDROCHLORIDE WITH ZINO DUST by GORDON DONG A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in the Department of Chemistry We accept this thesis as conforming to the standard required from candidates for the degree of MASTER OF SCIENCE. Members of the Department of gr. THE UNIVERSITY OF BRITISH COLUMBIA April, 1 9 5 6 . ( i ) ABSTRACT A dark red resin was isolated from the reaction mixture obtained by treatment of quincline hydrochloride with zinc dust. Indications, from chromatographic studies of the resin, that i t contained a number of different components led to extensive investigations of methods of separation. Satisfactory separation of the resin into pure components was f i n a l l y achieved by a scheme which essentially involved fractional extraction and fractional adsorption-desorption. Three pure components were isolated, and characterized by chemical and physical analyses. Two of the components were suggested as heterocyclic compounds of quinoline probably of polymeric nature. The third component appeared to be an aniline type compound resulting from reductive cleavage of quinoline. Ultra-violet spectra of the isolated pure components supported the deductions made from chemical and other physical evidence. Acknowledgment I wish to express my 8inoere thanks to Dr. K . Stark© for the invaluable advice which he has given me TABLE OF CONTENTS Chapter Page I ABSTRACT i II INTRODUCTION i i III HISTORICAL 1 IV EXPERIMENTAL 5 Synthesis 5 Preliminary Studies 7 Separation and P u r i f i c a t i o n of the Isolated Product 8 Analysis of the Isolated Pure Components 10 Experimental Results .... 2 1 V DISCUSSION 5 ° VI CONCLUSION 58 VII APPENDIX 59 Figures 59 Plates 4 ° Graphs ^ l VIII BIBLIOGRAPHY h h LIST OF TABLES Tabl© Pago 1 Performance Data of Experimental Developers 21 2 General Solubility of the Isolated Product 22 5 Adsorbent-Developer Combinations 25 4 Acetic Acid-Water Developers 2J 5 Methanol-Carbontetrachloride Developers 24 6 Developer Combinations for a Cellulose Column 24 7 Developer Combinations for a S i l i c i c Acid-Celite Column... 25 8 Relative Solubilities of the Components 25 9 Fractional Precipitation of Components 26 10 Fractional Extraction Solvents 26 11 Melting Point Result 27 12 R and Rf Values 27 15 Molecular Weight Results- 28 14 Elementary Nitrogen Test Results 29 15 Functional Group Test Results.. 29 16 Modification of Aqueous Acetic Acid Developers 52 LIST OF FIGURES Figure Page 1 Quinoline Hydrochloride Preparation Apparatus 39 2 Paper Chromatography Apparatus 8 LIST OF PLATES Plate X Column Chromatography. Apparatus 40 I I Fluorescence; under U.V. Light 40 LIST OF GRAPHS Graph 1 U.V. Absorption Curve for Component BY n 41 2 U.V. Absorption Curve for Component "0" 42 J. U.V. Absorption Curve for Component "RB ....... 4 5 ( i i ) INTRODUCTION It i s frequently observed that pure colourless quinoline when stored i n contact with impurities, that are reducing agents, gradually becomes intensely coloured. Furthermore, chemical reductions of quinoline are often accompanied by the formation of red coloured by-products, especially at elevated temperatures. Knowledge of the structure of these coloured by-products i B at present very limited. The general concept advanced mainly from the results of early investigations, i s that these coloured substances are quinoline dimers. During a course of research i n this department i t was observed that the hydrochloride salt of quinoline i n contact with zinc dust, produced an intensely red colour which increased rapidly on heating ( 1 0 ) . As i t appeared that a simple reaction yielded complex substances of undefined nature from a simple compound, investigation of this reaction product seemed worthwhile. Consequently, research was undertaken i n an attempt to establish the chemical and physical characteristics of this coloured product, and where possible, to correlate results with those obtained by previous workers for similar reactions of quinoline. HISTORICAL Research on the coloured by-products of quinoline, produced i n chemical reductions, have been neglected for the past f i f t y years. Our present knowledge of these compounds comes mainly from the research done i n Germany at the end ef the nineteenth and beginning of the twentieth century. The chemical reductions of quinoline investigated i n this period may be classified into two types. Those which employed the hydrochloride salt of quinoline and moderately reducing metals, such as, zinc and t i n ; and those using more vigorous reductants such as sodium, sodium amalgam and sodium amide. Belonging to the former class i s the work done by Glaus i n 1881, which i s of particular interest as his reduction is similar to the one under investigation. By heating quinoline hydrochloride with quinoline, or aniline, he obtained a red resin from which he isolated a yellow crystalline compound having a melting point of 114°C, assumed to be "diquinoline 1 1 (4). In 1878-79 i t was reported that Wischnegrasky obtained a small amount of a yellow resin which he believed to be "tetrahydrodiquinoline", from the reduction of quinoline with hydrochloric acid and zinc metal (17a) (17b). Wischnegrasky's reaction resembles the one under investigation with the exception that his reaction was performed i n an aque ous medium. At this time, others who investigated the products of quinoline produced i n reductions of similar nature were fcoenlg (9) and Vincenzi(l5). Prom their investigations a compound reported as "tetrahydrodiquinoline" was isolated. A number of workers obtained compounds known as "diquinolyl" and "diquinoline" from reactions involving sodium and quinoline. By treatment of quinoline with sodium metal, Williams obtained a compound which he regarded as "diquinoline" (16a) (16b) (O18H14N2). Contrary to this, Weidel investigated the same reaction and concluded that a "diquinolyl" was produced (OI8H12N2), having the structure of npy-l—-py-l diquinolyl" (15). However, a few years later Carl and Einhorn showed that the structure proposed by Weidel was incorrect (2). In 1920 Chichibabin and Zatezepina reported that a mixture of "diquinoline" and "diquinolyl" was formed as principal products i n the reaction of quinoline with sodium amide (5). According to the results obtained by these workers, i t appeared that the by-products formed i n chemical reductions of quinoline, are dimers of both quinoline, and of partially reduced quinoline. However, as their deductions were made on dubious evidence, the validity of their conclusions is question-able (6). Later researches on-quinoline have brought forth some evidence i n support of reductive cleavage ( l ) (7). A complete understanding of the reduction by-products of quinoline awaits future research. - 5 -EXPERIMENTAL I. 3ynthe8JB A. Preparation of quindine hydrochloride. Method -1 (anhydrous quinoline hydrochloride), (see Fig. 1, Appendix, for apparatus used) Into the reaction flask (A) containing 500-400 mis. of anhydrous ether (A.R.), 100 mis. of freshly purified synthetic quinoline (*') B„p. 256-257°C were introduced dropwise at the rate of 1 drop i n 5-4 seconds. Simultaneously, dry hydrogen chloride gas was passed into the ether at the rate of 0 . 2 - 0 . 5 c«c» per second and the ether solution was slowly stirred. Occasionally, when the quinoline hydrochloride precipitate became large, addition of quinoline and hydrogen chloride gas was stopped, and the reaction mixture was poured into the large funnel (G) from which the precipitate was f i l t e r e d off. The ether f i l t r a t e was returned to the reaction flask and the precipitation of quinoline hydrochloride was resumed. When the addition of quinoline was completed, the rate at which hydrogen chloride was bubbled into the reaction mixture was reduced to half the i n i t i a l rate and the size of the precipitate immediately formed was carefully noted. The reaction was stopped when a finer precipitate was obtained, which, when freshly formed, appeared as a cloudiness i n the ether solution. The precipitate of quinoline hydrochloride was washed free*of quinoline with several 50 ml. portions of anhydrous ether (A.R.) and dried i n a vacuum desiccator over P205» at a pressure of approximately 12 mm. Hg. (5)« The final product was a white, needle-like crystal-line solid of m.p. 135.540c. ( 5 ) . * Purified according.to procedure given by Vogel (14). Alternative method for preparing anhydrous quinoline hydrochloridet Dry hydrogen chloride gas was bubbled into freshly d i s t i l l e d quinoline (b.p. 2 5 7 ° 0 . ) until precipitation just began. The air space above the quinoline was saturated with hydrogen chloride gas and the reaction flask was stoppered and set aside. On standing, long white needles of quinoline hydrochloride appeared. The crystals were freed from excess quinoline by washing with benzene and dried i n a vacuum desiccator. The product had a melting point of 1 5 A ° 0 . Method-2 (quinoline hydrochloride hydrate) Forty grams of freshly d i s t i l l e d synthetic quinoline containing some cracked ice, was treated slowly with 1 0 mis. of concentrated hydrochloric acid (sp. gr. 1 . 1 9 ) . The reaction mixture was kept cold by the addition of more ice when necessary. The resulting solution was d i s t i l l e d u n t i l the water and excess quinoline was completely removed, leaving white crystals of quinoline hydrochloride hydrate, m.p. 94°C. ( 2 CpHyH + H2O) ( 5 ) . - 5 -B. Preparation of the product under investigation. 1. Reaction of quinoline hydrochloride with zinc dust. Twenty grams of freshly prepared quinoline hydrochloride (m.p. i52-54 0) were thoroughly mixed with 6 g. of zinc dust (A.R.). The mixture was heated under reflux at 200-210°0. for 4£ hours. The melt, i n i t i a l l y light yellow, became intensely red and increasingly viscous, until i t f i n a l l y s o l i d i f i e d into a dark red resin. 2. Isolation of the resinous product from the reaction mixture (I B 1.) F i f t y mis. of d i s t i l l e d water were added to the resinous mass and the mixture was warmed and stirred u n t i l the product loosen from the flask. The aqueous extract was decanted, and the residue was treated with another portion of d i s t i l l e d water. To the combined aqueous extracts, excess 10 N sodium hydroxide was added and the resulting solution was extracted twice with 25 ml. portions of chloroform. (*). The chloroform extracts were washed, then added to the residue previously obtained. On warming, the resin slowly dissolved i n the chloroform, giving a dark red solution. The chloroform solution was decanted and the remaining resin was dissolved by repeatedly extracting i t with fresh chloroform (50 ml. portions; 2-5 times). Small amounts of the product which remained with the unreaeted zinc were extracted with a l i t t l e hot methanol. The chloroform and methanol extracts were combined, and the combined extracts were thoroughly washed with d i s t i l l e d water, then gently evaporated to dryness. The dark red tar thus obtained, was dissolved i n 100 ml. of hot methanol (CP.). The resulting, methanol solution.was treated with 100 ml. of a 10% potassium hydroxide solution i n methanol, 60-80 ml. of d i s t i l l e d water, and then steam di s t i l l e d u n t i l a l l excess quinoline was removed. (*) Ethylbenzene is also suitable. The aqueous alkaline solution was decanted from the red amorphous residue and the residue was washed several times with hot water. 5* Alternative method for isolating the product from the reaction mixture (I.B.I.). The reaction mixture was extracted with chloroform until only unreacted zinc remained. The chloroform extract was evaporated to dryness and the resulting residue was dissolved i n concentrated hydrochloric acid. The acid solution was neutralized with sodium hydroxide, and the resulting precipitate of the product was f i l t e r e d off and washed with IN hydrochloric acid solution saturated with sodium chloride;. The purity of the isolated product was determined by crystallization and paper chromatography. - 7 -II. Preliminary studies on the Isolated product (I B 2) A. Attempted crystallizations of the isolated product. Various solvent combinations suggested by general solubility data of the product (Table 2, Expt'l Results) to be suitable for crystallization purposes, were tested. A l l attempts to obtain crystals from solutions of the product i n a large number of solvent combinations were unsuccessful. Inmost cases, only flocculent precipitates were obtained but, i n a few instances, fine powder-like precipitates were obtained at best. Fine powdery residues, apparently of crystalline nature, were obtained from extracts of the product i n the following "product soluble" solvents, with the use of the corresponding "product insoluble 1 1 solvents. However, on closer examination under a microscope these powders were found to be amorphous. "Product insoluble" solvents relative to "Product soluble" solvents 1. Diethyl ether Benzene 2. Pet. ether (30-60°) Acetone 3. Diethyl ether n- amyl alcohol 4. Pet. ether (60-110°) n - amyl alcohol 5. Pet. ether (30-60°) Diethyl ether - 8 2. Chromatographic study on the isolated product ( I B 2 ) Paper chromatograms of the isolated product were developed with the use of various solvent combinations, i n an arrangement as illustrated i n Fig. 2. Six such containers were used to produce paper chromatograms i n a series of tests. These containers were kept i n a large closed box i n order to avoid disturbances from temperature fluctuations. A'concentrated acetone extract of the isolated product was used i n obtaining the sample bands. Before paper chromatograms were developed, the containers were saturated with vapours of the developers for 12 hrs. Resolution of sample bands by neutral developers were frequently, detected through colour development with acetic acid vapour and by examination of the chromatograms under U.V. light. The paper chromatograms obtained, with an aqueous acetic acid developer, indicated that the product was a mixture of at least three different components. To confirm this observation attempts were made to find other developers which would produce similar results. Subsequently, a large number of solvent combinations were tested and a few were found which resolved the sample band. Data on the most successful developers for paper chromatography of the product ( I B 2 ) are given i n Table 2, Expt'l Results. In view of these results, i t was decided that the separation of the isolated product ( I B 2 ) into components as indicated by paper chromatograms, C o r v k a m e r Wha+man N44 I •filter paper \l.*nS mm. "teat tube UJIVK "Developer • i should be attempted* Throughout the remainder of this thesis, the three components isolated from the product ( I B 2 ) w i l l be known as follows: Band colour on a cellulose column when developed with dilute acetic acid  Component "Y" Component tt0a Component "R" yellow orange red - 10 -III Separation and purification of the isolated product ( I B 2 ) A. Scheme for the separation and purification of the isolated product ( I B 2 ) . 1. Solution of the product: The resin obtained i n Expt'l B 2 was repeatedly extracted with small portions of ethylbenzene ( a total volume of 125 mis. was required for 14 g. of resin ). The extracts were combined and washed several times with d i s t i l l e d water. Any remaining residue was dissolved i n excess acetone to which ethyl-benzene ( approx. 1/10 the volume of the acetone solution ) was added. The resulting acetone solution was slowly poured into a large volume of d i s t i l l e d water and the mixture shaken i n a separatory funnel and separated. The ethylbenzene layer was added to the main extract and the aqueous layer was discarded. 2 . Separation procedure: The ethylbenzene solution (from A I) was extracted several times with 100 ml. portions of 1:8 acetic acid-water solution u n t i l the extract was orange i n colour (approx. 400-500 mis.). The resulting ethylbenzene solution and the combined extracts were treated as follows: (a) Treatment of the ethylbenzene solution. The ethylbenzene solution (approx 150 mis.) was washed with d i s t i l l e d water u n t i l the washing was neutral. The washings were added to the original aqueous acetic acid extracts.- Sufficient s i l i c i c acid ( A.R. 100 mesh ) was added to cause complete decolouration of the ethylbenzene solution. (*)The sil. , i c i c acid with the adsorbed sample was a i r dried, and partially desorbed with 25 ml. portions of acetone ( A.R. dry) u n t i l the s i l i c i c acid was reddish orange i n colour. Desorption of the s i l i c i c acid was continued with a 2:1 acetone-pet. ether (5O-6O0) solution u n t i l the colour of the s i l i c i c acid - 11 -was orange. The s i l i c i c acid was dried and desorbed with a 1:5 acetic acid-water solution u n t i l colourless. The 1:5 acid extract was treated with 6N sodium hydroxide solution to a pH of 6.5 and the resulting solution was extracted with 4 0-50 ml. of ether. The ether extract was separated from the aqueous layer, washed, and evaporated to 5 ml., then added to 50 ml. of pet. ether (5O-6O 0). An orange flocculent precipitate was obtained (indicated by chroma-tographic analysis, to contain 90% of component "o"). The mixture was centrifuged and the orange precipitate was washed with pet. ether (5O-6O0). and dried i n a vacuum desiccator over P2O5. The combined acetone and acetone-pet. ether extracts were shaken with 4-5 g. of fresh s i l i c i c acid and then partially evaporated i n the presence of the s i l i c i c acid u n t i l the s i l i c i c acid became slightly red. The acetone solution was decanted and treated with 0.5-1 g. of fresh s i l i c i c acid. The s i l i c i c acid residues were combined and treated as before in (a) (v). The acetone solution was evaporated to dryness and the residue was dissolved i n 5 ml. of xylene (CP.). The xylene solution was washed once with water and was treated with pet. ether (50-60°) dropwise until precipitation just began. The brown-yellow precipitate was removed by centrifuging and treated according to procedure (c). The centrifugate was concentrated to 1 ml. and added slowly to 50 ml. of pet. ether (30-60°). A bright yellow precipitate was formed, which was centrifuged from solution, washed twice with pet. ether (20-60°) and dried i n a vacuum desiccator over P2O5. Further precipitation was induced i n the centrifugate by evaporation to half the volume. The resulting precipitate was combined with the f i r s t . The bright yellow precipitate contained 8 0 - 8 5 % - 12 -of component "R" according to chromatographic analysis (cellulose, adsorbents aqueous acetic acid, developer). (b) Treatment of the aqueous acetic acid extracts The combined aqueous acetic acid extracts were treated with sufficient 6N sodium hydroxide solution u n t i l the colour changed from red to reddish orange (pH approx. 2 . - 2 . 5 ) . The resulting solution was extracted with two (50 ml.) portions of xylene. The xylene extracts were combined and treated with s i l i c i c acid u n t i l no further adsorption occurred, (indicated by the colour of fresh s i l i c i c acid added). The s i l i c i c acid was treated as before i n part (a) (v). The extracted acetic acid solution was further treated with . 6N sodium hydroxide to a pH of 6.5 and extracted several times with xylene u n t i l the aqueous solution was colourless (a total volume of 250 ml. was required) and then extracted again with 50 ml. of chlorobenzene. The xylene and chlorobenzene: extracts were- combined and washed with d i s t i l l e d water unt i l the washings were neutral. The remaining aqueous solution was discarded. To the combined xylene-chlorobenzene extracts, sufficient s i l i c i c acid (A.R. 100 mesh) was added to adsorb the sample from solution completely. The s i l i c i c acid, containing adsorbed sample, was extracted with absolute methanol unti l the colour of the s i l i c i c acid was no longer yellow and then was treated , according to procedure (a) (v). The combined methanol extracts were evaporated to dryness and the resulting residue was dissolved i n a minimum volume (2-3 mis.) of xylene (CP.). Petroleum ether (3O-6O0) was added dropwise to the concentrated xylene solution and the buff coloured precipitate obtained i n the early stages of precipitation was collected and kept separate from the f i n a l yellow coloured precipitate. Both precipitates were washed with pet. ether (5O - 6 O 0 ) and dried in a vacuum desiccator over P2O5. The buff coloured precipitate was found to contain approximately 90% of component "Yn, and the yellow precipitate to contain 70% of component "Y" with J0$ of component nRfl. (c) Treatment of"the brown-yellow precipitate obtained i n part (a) (Separation procedure) The precipitate was dissolved i n n-butyl ether. The resulting solution was treated with acetone (approx. 1/10 the volume of the n-butyl ether solution) and then extracted with d i s t i l l e d water until the extracts were no longer coloured. The n-butyl ether solution was evaporated to a small volume and added to 50 vole, of pet. ether ( 5 O - 6 O 0 ) . A yellow precipitate, containing 70% of component "R" was obtained. Further purification of the precipitates of the different components was accomplished by column chromatography i n which a s i l i c i c acid (2)» celite (1) column ( " l " - 10 cm.: dia. - 3 cm.) and a acetone (1) : pet. ether (30r-60°^developer were used. The average time for development was 2-3 hrs. (1) S E P A R A T I O N P R O C E D U R E F L O W C H A R T Co) E t h i i l b e r ^ e n e S o l u t i o n (o,R) £tK^I benzene I - 6 E x t r a c t . Sil ic ic hcid S'» ic ic A c i i Adsorbent A c e t o n e / \££ . - tane - V e t - £tke| d « e o r p t l o n £tdnlb«ri-3en« S.l.< <JN. N a O H PH. fine Xylene fiol'n AcCi AQ. f>H Z-5 'belli C Y <«>) A c e t o n e . : P e t . E x t r a c t U ) 0 ) Xylene i : S t o ) i l l i c i t A c i d f e A e . r \ e . r a c t e < i S i l i c i c A c ' i d Partial evafln I A c e+ o p e ."Pet. E.tWe«-< t o l w . V i o n „ (,-p, jo) Elic i t Acio ("Treated a<J. U i f e r - ( discarded 6 M. H c p H X y l f r \ e - f k l o n o b e n - ^ t f n e o r MH^O H >ptl*\5 X i ( l e r K O r ^ n i k « J K C k l o r o b w y n c <w E x t r a c t i o n fiiUfei'« <\ci«i (2) F L O W C H A R T Co) S'llia'c. Adid h pH 4.S E-thep So I u+ion CO) Cone "Prtcip'(+a4e - oxatv^e-Componen-t " O " pet e+licr £30-<i3o_) fetVr - P e t -Sil ic ic Acid Acehjne. -.Ttet alW 9x.lu.-W CR) 0 ) *T r<» teasel a s in @ Combined Silicic Acid Acid 9»l* CR CO)) evapOrg-t-a b r o i u n - yellow Violent Solution of reViditf Ti»\al prec'ipf-fd+e bri£h.t ijallou Corriponerrt "'R* aqueous, «?cfva£-t Acetrme. n-ku.-k|t e+Kci- Concent rafe pet% /-Biet-H CJ1 Co>Tvponfin-t re^ ejrveipa"ta<l CY) S'll'icic. A c i d r e s i d u e Xylene . Xylene. Solution aid "Vo SO pc4. eMvur pY«cip»4a4e - \>u-ff Co\ourei C o m p o n e n t " y ' B. Column chromatographic separation The product from I B 2 was separated on a small scale into pure components by column chromatography. Procedures for the most effective chromatographic systems are presented. 1. Cellulose powder (adsorbent) - aqueous acetic acid (developer) method. Apparatus: see Plate I, Appendix. Temperature(room): 19-21°C. Adsorbent: Whatman cellulose powder for chromatography. Adsorbent column, length: 56 cm., diameter: 4-4 cm. Column packing: Both wet and dry packing were employed. Sample solution: 0.2-O.Jg. of the product from I B 2 were dissolved i n ^  ml. of glacial acetic acid and diluted to 10 ml. Development procedure: The column of cellulose was allowed to stand i n d i s t i l l e d water for 24 hrs. before i t was used. The level of the water i n the column was adjusted to a height of 1 cm. above the cellulose. The sample solution was carefully introduced into the water above the cellulose and the resulting solution was gently stirred. Water was released from the column u n t i l the surface of the sample solution just covered the adsorbent. D i s t i l l e d water was introduced to a height of 4-5 c m « above the cellulose and the level was readjusted to a height of 1 cm. The column was f i l l e d within 4-5 cm. of the top with the proper aqueous acetic acid developer (Table 4, Expt'1 Results) and the developer reservoir, also f i l l e d with the developer, was attached to the top of the column. The developer was then allowed to flow through the column. By employing a series of acetic acid-water developers, (Table 4, Expt'l Results) according to the order given, the applied sample band was resolved - 1 7 -into three distinct banda of different colours (descending order: red, orange, yellow) and i n turn, eluted. The component i n each fraction was removed from solution by neutral-ization of the acetic acid with 6N sodium hydroxide, extraction of the component from the resulting solution with benzene, and fi n a l l y , precipitation of the component from the extract with pet. ether (50^-60°). 2. S i l i c i c acid - celite (adsorbent) and methanol-carbon-tetrachloride (developer) method. Apparatus: See Plate I, Appendix. Temperature(room) » 19-21°0. Adsorbent column, length: 25 cm., diameter: 4.4 cm. Column packing: Purified uniform, coarse c e l i t e was prepared in the following manner:-Three pounds of celite (tech.) were added to four l i t e r s of d i s t i l l e d water, which was previously acidified with 5N hydrochloric acid (100 ml. to 4 1. of water) and stirred for 10-15 minutes, then allowed to stand for 5 minutes. The resulting suspension of fine c e l i t e was decanted from.the coarser celite that had settled. Water was added and the screening process repeated u n t i l no cel i t e remained suspended after 5 minutes. The screened celite was washed free of acid and dried overnight at 1 5 0 - 1 4 0 ° C . Four hundred and f i f t y grams of s i l i c i c acid-celite adsorbent was made by mixing 2 parts by weight of s i l i c i c acid (100 mesh, A.R.) with 1 part of processed c e l i t e . A surry of the adsorbent mixture i n carbontetrachloride was made and poured into the column (with the outlet tube closed). The mixture i n the column was stirred while solvent flowed out of the column. The adsorbent settled to the bottom as a firm, uniform packing. - 18 -Sample solution: 0.5 - 1.0 g. of the product from I B 2 were dissolved i n 5 ml. of benzene (ethylbenzene is also suitable). Development procedure: The carbontetrachloride above the adsorbent column was adjusted to a height of 1 cm. The sample solution was added to the carbontetrachloride above the adsorbent and the resulting solution was stirred. Sufficient solvent was allowed to flow through the column to bring the level of the solution just above the packing. Ten ml. of a displacer solution, methanol (.1): carbontetrachloride (1), were introduced and the level readjusted close to the surface of the adsorbent column. The column and reservoir were f i l l e d with a methanol ( l ) : carbontetrachloride (3) developer and the column was assembled (see Plate I, Appendix) and set into operation. The sample band was resolved into three bands, yellow, orange and red, i n descending order and, i n turn, collected i n fractions from the column. Fractions of each band were concentrated by slow evaporation and the component in each was precipitated with pet. ether (50-60°). Performance data of practical mixtures of methanol-carbontetrachloride, as developers on a s i l i c i c acid (2): celite ( l ) column, is given i n Table 5» Expt'l Results. Data on other developers which may be used on this adsorbent is presented i n Table 7» Expt'l Results. The maximum separation capacity of the s i l i c i c acid (2): celite (1) column when used with methanol-carbon tetrachloride developers, was found to be 1-1.5 g. of sample (I B 2 ) per run. Other promising adsorbent-developer combinations are presented i n Table 5, Expt'l Results. - 1 9 -Samples of component "Y", "O" and "R" obtained by column chromatography were of high purity. C. Other methods of separation investigated. Extensive studies were made on a number of methods which were less successful due to various limitations. Brief descriptions of them are included in the following: 1. Fractional precipitation (a) From aqueous acid solutions A dilute acetic acid solution of the isolated product ( I B 2 ) was treated with 6N ammonium hydroxide and the precipitates of each component were collected at different pH ranges (see Table 9» Expt'l Results). Precipitation from 12N hydrochloric acid was also examined. 7 0 % separation was the maximum obtainable by this method. (b) From organic solutions Organic solutions of the isolated product ( I B 2 ) were treated with organic precipitants i n attempts to effect fractional precipitation of each component. The solvent-precipitant combinations were chosen according to solubility data given i n Tables 2 and 8, Expt'l Results. This method was less effective than method (a) 2. Fractional extraction From solutions of the product ( I B 2 ) i n various organic solvents, the components of the product were selectively extracted with aqueous acetic acid solutions of the proper strength, Table 1 0 , Expt'l Results. Separations achieved by this method were good. However, this method was slow and involved large volumes of aqueous extracts. - 20 -IV Analysis of the isolated component a ( i l l A ) The following experiments were conducted on samples of the components obtained from the separation scheme (III A). These samples were further purified by column chromatography, and were approximately 90-95% pure according to paper chromatograms. A. Physical characterization. 1. Melting point determination. Melting point determinations were performed with a copper heating block. 2. Molecular weight determination. Molecular weights were determined by the Rast (cryoscopic) method according to the procedure given by Niederl and Niederl (11). Pure camphor (A.R. resublimed) of m.p. 180°C, with a depression constant of K e 59*700 (standardized with naphthalene m.p. 80°C) was used. The melting point of each sample was redetermined 5-4 times i n succession for constancy. 5. R and Rf values. The R and Rf values of the pure components were determined from the bands obtained i n a complete chromatographic development of product ( I B 2 ), effected on cellulose adsorbent (powder and paper) by acetic acid-water developers. 4. Ultra-violet absorption. The U.V. spectrum of each pure component (absolute methanol solution) was determined on a Beckman D-&-4 recording spectrophotometer. B. Chemical characterization Each pure component was analyzed for nitrogen (qualitative) and the following functional groups: -NH2, * NH, - N7 -C = O-, -OH and -C = 0 according to procedures given by Fuson and Shriner (8) - 21 -Table 1 Performance Data of Experimental Developers, Adsorbent: cellulose Form: paper stripe (Whatman #1) Sample: Product from I B 2. No. Experimental Developer (Volume Ratio) Average Developing time (hrs.) Separation 1 Acetic acid: Water (5) r (7) 14 excellent 5-distinct spots (a & b) y, o, r 2 Acetic acid: Water (5i) *• (7) 17 as above 3 Chloroform: Ligroine (5) « (7> 8-9 excellent 3**di 8tinct spots (a) o, y (b) o, r, y k> Benzene: Ligroine (5) • (7) 9-10 good 5-distinct spots (a) o, y (b) o, r, y 5 Methanol: Ligroine (7) : (5) 9-10 2-distinct spots (a) n i l (b) o, r 6 Methanol* Ligroine (6) r (4) 6 (same as for 7:5) lower developing capacity 7 Ethyl acetate (3): Ligroine (7) 8-10 2-spots (a) o, y (b) o, r 8 n-iPropanol: Ligroine (5) : (95) 6 24 2-distinct spots (a) n i l (b) o, r 5-distinct spots (a) n i l (b) o, y, r 9 Methanol (2): Chloroform (2): Ligroine (6) 12-13 5-spots (a) n i l (b) o, r, y Notation: No. - most satisfactory developers "a" - colour as developed "b" - colour by acetic acid vapour development "y" - yellow, "o" - orange, " r n - red. - 22 m Table 2 General Solubility of the Isolated Product ( I B 2 ) Legend: /- very soluble /- /- soluble low solubility - insoluble . Solvent B.P. F.P. Solubility °C. °C. Water 100 0 Petroleum ether 50-60 -Petroleum ether 60-110 Cyclohexane 80-7 6.5 -(/") Carbon tetrachloride 76.8 -22.9 n-Butyl ether 142.4 -97.9 Ethyl acetate 77.2 -85.6 •h n-Amyl alcohol (cold) 158.1 -78.9 -h Diethyl ether 54.6 •h Acetone 56.2 -94.8 Benzene 80.1 5.5 -H-n-Propanol 97.2 -127.0 -hh Dioxan-1,4 101.4 11.8 -hh n-Octyl alcohol 194.5 -16.7 -H-cone. Hydrochloric acid A A Methanol 64.7 -97.8 -hH-Chloroform 61.5 -65.5 •hH-Ethanol 78.4 -114 .5 -h-h-h n-Butanol 118.0 -89.8 -H~h Ethylbenzene 156.2 -95.0 -H-f-n-Amyl alcohol (hot) 128.1 -78.9 +++-Ethylene glycol 197.9 -15.6 Chlorobenzene 152.0 -45.2 aq. Acetic acic (>6N) Values of B.P. and F.P.-from Lange'a "Handbook of Chemistry" 1955* - 25 -Table 5 ADSORBENT - DEVELOPER COMBINATIONS FOR CHROMATOGRAPHIC SEPARATIONS Adsorbent Developer Magnesia (2):Celite (1) Alumina Celite (coarse) Chloroform : Pet. ether (30-60°) Pet. ether (30-60°) : Chloroform Acetone t Pet. ether Bands developed by these systems were detected by U. V. light. jTable 4 ACETIC ACID - WATER DEVELOPERS, CELLULOSE COLUMN Sample) Product from I B 2. Developer Acetic acid: Water (vol. ratio) Component developed and eluted Development & Elution approx.- time - hrs. D - 1 1 : 18 Y 4-5 D - 2 1 : 8 0 2 - 5 D - 5 1 : 5 R 3 - 24 -Table 5 METHANOL - CARBONTETRACHLORIDE DEVELOPERS ( S i l i c i c Acid (2): Celite (.1) column) Sample: Product from I B. 2. Approx. Methanol : Carbontetrachloride Band average. Displacer Developer order - colour - component Elution (vol. ratio) (vol.ratio) (ascending) time hrs. 1 : 2 1 i 3 1 red "R" 2 - 5 • 2 orange "O" 4 5 yellow 5 2 : 1 1 : 5 1 red "R" 4 2 orange n 0 n % 5 yellow nyn 5 Note: Band colours are given as they appeared on the column. Table 6 DEVELOPER COMBINATIONS FOR A CELLULOSE COLUMN Sample: Product from I B. 2. Developer Component - Order of (vol. ratio) Development & Elution Benzene : Pet. ether (60-110°) "O" - 1st. (2 .5) i (7.5) "Y" - 2nd "R" - 3rd Chloroform : Pet. ether (60°-110°) (2) : (8) n 0 n - 1st "YH - 2nd - flRn - 3rd Methanol (3) : Chloroform ( l ) : B0" - 1st Pet. ether (60-110°) (6) "T" - 2nd "R" - 3rd Note: Band order was determined by colour development with an Acetic acid (1) » Pet. ether (60-110°) (90) solution. - 25 -Table 7 DEVELOPER COMBINATIONS FOR A SILICIC ACID (2) s Celite Column ( l ) Developer Band (vol. ratio) order - colour - component (descending) Acetone : Pet. ether (50-60°) l e t orange "O" CD • (2) 2nd red 5rd yellow Chloroform t Carbontetrachloride l e t yellow B y It (1) i <*.) 2nd red "R" 5rd orange "0" (2) i (1) 1st yellow B y B 2nd orange "O" 5rd red nRit Table 8 RELATIVE SOLUBILITIES OF THE COMPONENTS Samplet Product from I B 2 Solvent Relative Solubility {% of the extracted product) Component! Y 0 R Benzene 40 4o 20 Toluene 25 60 15 Chlorobenzene 45 40 15 Ethylbenzene 20- 60 20 n-Butyl ether 50 20 50 Ether 25 50 25 Xylene 15 55 50 Note: The values of % component extracted were estimated from chromatograms of. the product I B 2. - 26 -Table 9 FRACTIONAL PRECIPITATION OF COMPONENTS Component Maximum Precipitation pH Interval B R B 5.2 - 5.5 "0" 5.0 - 5.2 7.0 - 8.0 Note: These values were obtained for fractional precipitation from dilute acetic acid solutions. Table 10 AQUEOUS ACETIC ACID FRACTIONAL EXTRACTION SOLVENTS Component Extraction order solvent HOAc s H20 ByB 1st 1 J 60 B Q B 2nd 1 « 15 Note: 1) Component nRn, remaining i n solution, was precipitated with pet. ether (50-60°). 2) The above extraction solvents are suitable for samples containing approximately equal amounts of each component. 5) Sample solvent: Xylene (CP.) - 27 -Table 11 MELTING POINT RESULTS Component m. p. °C By It 114 - 115 "0n 198 - 199 "R" 161 - 163 Table 12 R AND R f VALUES Component R R f tlylt 1.21 0.92 "0" 0.89 0.87 n R n 0.07 0.78 Note: Rf values - adsorbent : cellulose (paper strips) developer : acetic acid (j£) : Water (7) aver, time: 17 hrs. R values - adsorbent : cellulose (powder) developer : acetic acid 1 ( l ) : water (8) - 28 -Table 15 MOLECULAR WEIGHT RESULTS Method: Cryoscopic (Rest) Solvent: Camphor K * 59»700, m.p. = 180°C. Component "Y" Sample - 1 Mol. wt. - 595 Sample - 2 Mol. wt. - 415 Average Mol. wt. - 404 Formula Theoret. Mol. Wt. Expt'l Mol. Wt. % Deviation 2 (C9H7N) 258 56.5 5 (C9H7N) 587 4.4 4 (C9H7N) 516 21.7 Component "O" Sample - 1 Sample - 2 Mol. Wt. - 292 Mol. Wt. - 295 Average Mol. Wt. = 295 Formula Theoret. Mol. Wt. Expt'l Mol. Wt. % Deviation 2 (C 9H 7N) 258 15.6 5 (0 9H 7N) 587 24.5 4 (C9H7N) 516 45.2 - 29 -Table 14 ELEMENTARY NITROGEN TEST RESULTS Component Results B Y " «o" "R" +• Note: Tests were conducted according to the sodium fusion procedure. Table 15 FUNCTIONAL GROUP TEST RESULTS Group Test Results Component: Y 0 R NH2- Hinsberg Lieberman Nitroso NHs Hinsberg Lieberman Nitroso - - --NS Hinsberg Lieberman Nitroso + + -C-C- Permanganate oxidation (slow arom (slow arom -f~ ) (fast aliphatic) -0H Ceric Nitrate . Lucas - - M -CaO Phenylhydrazine -m JO «• DISCUSSION In the preparation of quinoline hydrochloride, proper control over the introduction of the hydrogen chloride gas was essential i n order to prevent formation of the fuming hydrochloride (C7H0N - HCl) f KC1 (5). The presence of zinc chloride i n the reaction mixture obtained by treatment of quinoline hydrochloride with zinc dust, indicated that reduction had occurred. As no hydrogen gas was released during the reaction, i t appeared that, i n the formation of the red product ( I B. 2.), reduction of quinoline was involved. Later research, as w i l l be brought out, indicated that this was true. The amount of zinc consumed by reaction with quinoline hydrochloride was found to be approximately equal to that required for complete reduction of the hydrogen involved i n salt formation with the basic "N" of quinoline. It was found that the hydrate of quinoline hydrochloride could be used i n place of the anhydrous compound without serious complications, provided the reaction temperature was sufficiently high, (210-220°C.). Complete removal of excess quinoline from the reaction product was essential i n order to avoid complications later i n separating i t into pure components. Removal of excess quinoline by steam d i s t i l l a t i o n was not completely satisfactory, for a considerable amount of the product was lost through solution. Furthermore, there was the danger that the product i n sodium hydroxide solution might undergo degradation. It was observed i n later experiments that sodium hydroxide solution does degrade the reaction product into alkalinesoluble substances having a strong pungent odour similar to that of nitrobenzene. These d i f f i c u l t i e s were largely overcome by adding a considerable amount of sodium chloride to the solution before d i s t i l l a t i o n and performing the d i s t i l l a t i o n over a short period without using large excess of a l k a l i . Although the alternative method involving precipitation from concentrated hydrochloric acid solution does not have these objections, i t is less e f f i c i e n t i n removing excess quinoline than the steam d i s t i l l a t i o n procedure. Separation of the crude product into three purified components was extremely d i f f i c u l t due to close similarities i n the chemical and physical properties of the components. Conventional methods of separation were not satisfactory. Many of them gave poor separations, whereas others, which gave good separations, had the limitations of low capacity and long separation periods. The main objective i n the separation of the crude product was to effect a good separation, on a large scale, within a reasonably short period. As none of the conventional methods were completely satisfactory, i t was hoped that effective parts of a number of methods could be incorporated into a satisfactory separation scheme. The scheme; of separation, as given i n its.-' present form f u l f i l s , to a large extent, the necessary requirements. This procedure was based essentially on a crude preliminary separation of the components by fractional precipitation and fractional extraction, followed by a series of purifications i n which methods with increasing sel e c t i v i t i e s , such as, finer fractional extractions, batchwise adsorption and desorption, were successively employed. In general, increase i n sensitivity was accompanied by a decrease i n capacity. In the scheme presented, extraction with 1:8 acetic acid-water solution effects a preliminary removal of the „ "IT1', component from the solution of the crude product. Fractional extraction of the 1:8 aqueous extracts, with xylene, at the adjusted pH of 2-2.5, removed most of the ." Ou" and MR1'components - 22 -which ware co-extracted with component "Y'.' Further treatment with a l k a l i to a pH of 6.5-7.0 released the ,. »Y'«. component which was extracted from the aqueous solution with xylene. In order to avoid complications the pH of the aqueous extracts was maintained below 7. Final stages of purification of the component were effected by selective adsorption and desorption from s i l i c i c acid, using properly chosen solvent combinations. Preliminary separation of the two components remaining i n the ethylbenzene solution was also carried out by fractional extraction of the component nR B with a 1»4, acetic acid - water solution. Both methods were equally effective, however, the adsorption-desorption procedure was more convenient. Subsequent purification of component "0" and nR" was performed through a series of adsorptions and desorptions i n which various mixtures of acetone-petroleum ether were employed. Caution was taken to avoid acid fumes when precipitating the isolated components from organic solutions, as these components were found to be acid sensitive. The series of aqueous acetic acid developers presented i n Table A, Expt'l Results, was suitable for development of samples which contained approximately equal amounts of each component. With samples which were exceptionally rich i n one component such as those treated for purification, modification of the strengths of these developers was necessary. Table 16 MODIFICATION OF AQUEOUS ACETIC ACID DEVELOPERS Sample Developer of Modified Ratio (Vol) Component i n Component HOAc - H20 High % Yellow "T", D»l 1 - 25-30 Orange "0", D-2 1 10-15 Red "0% D-2 1 - 5 - 55 -High flow rates, such as, 1 drop/sec. were usually required for satisfactory separations on the s i l i c i c acid-celite column with methanol-carbontetrachloride developers. It was generally found that chromatographic separations proceed most satisfactorialy by a slow i n i t i a l development of the sample band, followed by rapid elution of resolved bands. In addition to chromatographic methods, batchwise adsorption-desorption methods were frequently used for purification of samples. With s i l i c i c acid adsorbent i t was found that the selectivity of this method may be adjusted by using suitable organic solvent combinations. With cellulose adsorbent, selective adsorption was controlled by adjusting the pH of the acetic acid solution of the product. In the above adsorbent-solvent systems, progress of separation was indicated by the colour of the adsorbent. (Bright red for component nR"; orange for component "0"j and yellow for component n Y H ) . The pure components isolated were light coloured, amorphous, hydrophobic solids. Their i n s t a b i l i t y i n absolute methanol was clearly indicated by the fact that the U.V. spectra of solutions of the isolated components were altered after a few days (see Graph 1 & 5 ). The belief, based on colour theories of organic molecules, that the component which gave a yellow acetic acid solution has the shortest conjugated system, and the one which gave a red acetic acid solution has the longest, was supported by U.V. absorption data. The components in product I B.2. appeared to be reduced forms of the corresponding components of the product formed from quinoline hydrochloride under non-reducing conditions ( i . e . in the absence of zinc). - 3 4 -It was observed that by refluxing product I B.2. i n n-amyl alcohol for 6 - 8 hrs. this product gave a chromatogram (aqueous HOAc developer) with the same Rf values as those obtained from the chromatogram of the product formed without zinc. * Solutions of pure component nY" and pure component "R™ i n benzene and methanol showed fluorescence of different oolours. In daylight, solutions of component "Y" fluoresced reddish-purple, and solutions of component "R" fluoresced greenish-yellow. Under Ultra violet light, fluorescence was more intense and was blue i n the solution of component nY n and yellow i n the solution of component "R" (see Plate II, Appendix). Fluorescence persisted i n solutions of these eomponentB over long periods of time without apparent decrease i n intensity. The U.V. spectra of these solutions indicated that the solution with greenish-yellow fluorescence (Component "R") exhibited low U.V. absorption, while the other with reddish-purple fluorescence (Component "t") exhibited high U.V. absorption. The U.V. absorption spectra of these solutions are given i n Graphs 1 & 3, Appendix. As the complete structure of these components are unknown, proper explanations for this effect can not be given at this time. From the close agreement i n melting points, i t appeared that component HY n was identical to the compound obtained by Claus (m.p. l l4°C) (4) . As the reactions by which each was formed are similar, i t seemed probable that identical compounds were produced. Supporting this view is the fact that their Rf values were also i n close agreement. The melting point of component "R" (m.p. 162°C.) is i n excellent agreement with that reported by Koenig for * From the chromatograms of the product I B.2. and of the product formed without the use of zinc, i t was evident that the components obtained i n the reaction with zinc have much closer solubilities than the corresponding components obtained without the use of zinc. It follows therefore, that the components i n product I B.2. are more d i f f i c u l t to separate than those i n the product obtained i n the absence of zinci This was found to be the case. - 55 -"tetrahydrodiquinoline" (m.p. 161-62°C) (9). Close similarity of their chemical properties i s further evidence which suggests component "Rn to be identical to Koenig's compound. Production of a compound identical or similar to component "Rn in Koenig's reaction might be expected i n view of the fact that reactants employed i n both reactions are essentially the same., The experimental molecular weight of component "Y" corresponds to that of three quinoline nuclei, while that of component "0" i s i n agreement with the weight of two quinoline nuclei. The molecular weight results, together with the fact that quinoline was the only organic reactant employed, seemed to indicate that component "Y" is a quinoline trimer and component "0" is a quinoline dimer. Later findings from amine nitrogen type tests and U.V. spectre, showed that these assumptions were jus t i f i a b l e . Due to solution d i f f i c u l t i e s no satisfactory results for the molecular weight of component "R" were obtained. Most satisfactory reproductions of molecular weights of the components were achieved by using dilute camphor solutions of 1:50 concentration or less. Many structural features of the isolated components were disclosed from characterization -tests. The presence of tertiary nitrogen i n components "Y" and "0" evidently implies that the heterocyclic rings i n these components are uncleaved. It appeared that the synthesis of these components did not involve reductive cleavage of the heterocyclic ring i n quinoline. Evidence in support of tertiary nitrogen i n component "Y" and "0" was also obtained from the results of permanganate oxidation. The slow rate of oxidation of component "Y" and "0" suggested that a moderately stable group such as the benzonoid ring of quinoline, rather than ethylenic bonds, or primary, secondary amines which would arise from - 56 -reductive scission of quinoline, was oxidized. Positive indications of primary amine nitrogen i n component "Rn suggested that reductive cleavage of the heterocyclic ring of quinoline was involved i n the formation of this component. According to the rates of oxidation of the components, their relative s t a b i l i t y are i n the order: Evidence i n support of many of the deductions made from analytical results were obtained from the U.V. spectra of the isolated components. Presence of the quinoline nucleus, SB the basic structural unit, i n component nY n and "0n was inferred from the fact that'these components exhibited maximum U.V. absorption at the same regions as quinoline with the exception of a small shift of the central peak. Thie shift is understandable as the quinoline nucleus is l i k e l y to be modified by the structures of the components. For this reason, the differences i n the shapes of corresponding absorption peaks are also to be expected. The similarity of the U.V. spectrum of component "Y" and of component n0" with that of free quinoline appeared to be i n favour of polymeric structures for component "Y" and "O", having quinoline as the basic repeating unit. This was also suggested by molecular weight results. The fact that the absorption peak at 520Wm u was absent from the U.V. spectra of the n(R." component suggested that its structure i s basically different from those of component "Y" and n0 n. It was deduced from chemical analysis of component nR n that the formation of component "R" involved reductive cleavage of the heterocyclic ring of quinoline. Consequently, this would produce an aniline type nucleus. - 57 -The U. V. spectrum of component "R" was found to resemble that of free aniline i n that i t has the same number of absorption peaks as the spectrum of aniline and that one of the peaks corresponds to one i n the spectrum of aniline. However, the other was shifted considerably. This shift may be accounted for by structural modifications imposed on the aniline nucleus. - 38 -CONCLUSION Presence of at least three different components In the red product formed from the reaction between quinoline hydrochloride and zinc was indicated and repeatedly confirmed by chromatography. Separation of the product into pure components was most satisfactorily achieved on a large scale by a separation scheme based on fractional extraction and fractional adsorption-desorption; and on a small scale by column chromatography. The isolated pure components were light coloured, amorphous, non-hygroscopic, strongly basic solids, which were soluble inmost organic solvents. Each component exhibited different colours i n aqueous acetic acid solutions and on s i l i c i c acid adsorbent. From chemical and physical analysis, components "Y" and "0" appeared to be polymeric substances of quinoline (Component "Yn, a trimerj component "O", a dimer), while component "R" appeared to be an aniline type compound, possibly of polymeric nature. However, aa component nR n was the least stable and most insoluble, conclusions made on its structure must be taken with reserve. - 3 9 -A P P E N D I X 150 ml. P r e p a r a t i o n of Quinoline h^drockloy-iole A p p a r a t u s -40-P l a t e - I I P l a t e - I Column Chromatography Apparatus 100 <\o -80 -§ *>-P o to S -5° in ^ 40 30 10 U-V ABSORPTION SPECTRUM OF COMPONENT " Y" S o l v e n t : abs>. V- /\e -tKano\ g »-<apK , \nrV\aU\j «\rapW .cv^er •Sdcvjs I I H IO J I I L _ J L 140 X 5 0 X60 17 O 280 2<tO 300 3 IO 310 330 3 40 X IO 1 "WAVE L E N G T H m^l U.V. ABSORPTION SPECTRUM OF COMPONENT "O' Gv-apVi, \nWia\Vj Q r a p r x , ctf ter 5 eAa^S> 21D ISO 2.40 2.50 260 2.70 Q.60 2SO 300 3 IO 3Z0 330 340 P 1 I JO 220 U.V . A B S O R P T I O N S P E C T R U M OF C O M P O N E N T *TV' 230 240 2SO 260 270 20O X9Q 300 310 320 330 340 X t O 1 WAVE L E N G T H myU ADDENDUM OaLumn Chromatography Data Developer Acetic acid:Water 1 : 18 (D-l) 1 : 8 (D-2) 1 : 2 (D-2) Chloroform:Pet. ether(60-110°) 2 : 8 Benzene: Pet. ether(60-110°) 2.5 : 7.5 Methanol(2):Chloroform(1): Pet. ether(60-110°)(6) Methanol:Carbontetrachloride 1 : 2 A^prox. Flow rate (o.cX/min.) 1.0 1.5 1>5 1.5 r.o Adsorbent cellulose powder cellulose powder cellulose powder cellulose powder cellulose pov/der 1»5(initial 2 hrs.) cellulose 1.0( final 2-2 hrs.) powder Acetone:Pet. ether(60-110 ) 1 : 22 2.0 2.0 0.4-0.5 Chloroform:Oarbontetrachloride 1 : 4 5.0-6.0 2 : 1 5.5 s i l i c i c acid(2): celite(l) s i l i c i c acid(2): celite(l) s i l i c i c acid(2): celite( 1) (column of length - 10 cm})' si l i c i c acid(2): celite(1) s i l i c i c acid(2): celite(1) Note : The s i l i c i c acid-celite column was prewsjshed with a chloroform( 1):oarbontetrachloride(2 or 2) solvent mixture, before the above chloroform:carbontetrachloride developers were used. - 44 -BIBLIOGRAPHY 1. Braun, J.V., Ber. 46, 5169-82 (191J) c.f. C.A. 7_, 129, 2567. 2. Carlier, E. and Einhorn, A., Ber. 2J, 2894-96, (1890). 5. Chichibabin, A.E. and Zatzepina, E.V. J.Russ, Phys. Chem. Soc. 5_0, 552-7 (1920) c.f. C. A. 18, 1502 (1924). 4. Claus, A., Ber. 14, 1959 (1881). 5. Eckstein, 0. Ber. 2_9_, 2156-7 (1906). 6. Elderfield, R. C , Heterocyclic Compounds, John Wiley & Sons, Inc., New York, 1952, Vol. 4, pp. 271-75." 7. Emde, Hev. Chim Acta., 15_, 1520 (1952); Ann., 591. 88 (1912). 8. Fuson, R.C. and Shriner, R.L., The Systematic Identification of Organic Compounds. John Wiley & Sons, Inc., New York, (1948). 9. Koenig, W., Ber. 14, 99 (1881). 10. Mi tenner, H., M.Sc, Thesis, University of British Columbia, (1952) 11. Niederl, J.B. and Niederl, V., Micromethods of Quantitative Organic Analysis, John Wiley & Sons, Inc., New York, (1951). 12. Orchin, M. and Friedel, R.A., Ultraviolet Spectra of Aromatic Compounds, John Wiley & Sons, Inc., New York, (1951). 15. Vincenzi, Gazzetta Ohimica Italiana, 24, II, 98. 14. Vogel, A. I., A Textbook of Practical Organic Chemistry Longmans, Green and Co., London, (1948), pp. 787. 15. Weidel, Monatsh, 2, 491 (1881). 16. a Williams, C. G., Chem. News, 27_, 85 (1878). 16. b Williams, CO., Chem. News, 4j_, 145 (1881). 17. a Wischnegradsky, A., ed. G. Wagner, Ber. 12, 1480-92 (1879). 17.b Wischnegradsky, A., ed. Krakaus, Ber. 12_, 25IO, 2400 (1880). 

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