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The acid component of jute hemicellulose Rogers, Ian Henry 1958

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THE ACID COMPONENT OF JUTE HEMICELLULOSE  by IAN HENRY ROGERS B.Sc,  Queens U n i v e r s i t y , B e l f a s t , N. I r e l a n d ,  A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE  i n the Department of Chemistry  We accept t h i s t h e s i s as conforming t o the required standard  THE UNIVERSITY OF BRITISH COLUMBIA November, 1958  1954  ABSTRACT Defatted powdered jute vas delignified by chlorite treatment and the hemicellulose extracted v i t h a l k a l i .  The precipitated material vas  purified by washing with alcoholic hydrochloric acid and dried by s o l vent exchange. The hydrolysed hemicellulose yielded neutral sugar and sugar acids separated on ion exchange resins. The neutral sugar was identified as D-xylose.  The sugar acid fraction contained mainly an aldobiouronic acid  proved by the reduction of the methyl ester methyl glycoside with lithium aluminum hydride followed by hydrolysis to consist of D-xylose linked to a monomethyl glucose.  This was shown, v i a i t s ahilide and osazone, to  be 4-0-methyl-D-glucose. Methanolysis of the aldobiouronic acid yielded the methyl glycoside of a uronic acid which on treatment with diazomethane and then with methanol ic ammonia gave 4-Oj-methyl-oC-D-glucuronoamide methyl glycoside, after fractional c r y s t a l l i z a t i o n . Reduction of the aldobiouronic acid methyl ester methyl glycoside with lithium aluminum hydride, followed by methylation and hydrolysis, gave 2,3,4,6-tetra-0_-methyl-D-glucose and 3,4-di-O-methyl-D-xylose. A search for a crystalline derivative of the purified aldobiouronic acid and of i t s related x y l i t o l compound formed on reduction with potassium borohydride was  unsuccessful.  In presenting  t h i s thesis i n p a r t i a l fulfilment of  the requirements for an advanced degree at the  University  of B r i t i s h Columbia, I agree that the Library s h a l l make i t f r e e l y available for reference  and study.  I further  agree that permission for extensive copying of t h i s thesis for scholarly purposes may  be granted by the Head of  Department or by his representative.  my  It i s understood  that copying or publication of t h i s thesis for f i n a n c i a l gain s h a l l not be allowed without my written permission.  Department of The University of B r i t i s h Columbia, Vancouver 3, Canada. Date  ACKNOWLEDGEMENT I wish t o express my s i n c e r e thanks to Dr. G.G.S. Dutton f o r h i s patience, advice and encouragement i n d i r e c t i n g t h i s research work.  TABLE OF CONTENTS Page Historical Introduction  1  The Identification of Uronic Acids  8  The Acids i n Jute Hemicellulose  11  Experimental  22  Jute Hemicellulose  22  Jute Aldobiouronic Acid  24  Bibliography ,  40  TABLES Table I  -  Table II -  Aldobiouronic Acids of Proven Structure  4  Aldobiouronic Acids of Uncertain Structure  7  HISTORICAL INTRODUCTION Land plants usually contain several types of polysaccharide materi a l other than cellulose which i s their main support structure.  These  may be described as "homoglycans" where only one type of monosaccharide i s present i n the structure as for instance i n starch or inaulin or as "heteroglycans" where more than one type of monosaccharide residue occurs. These latter materials have been c l a s s i f i e d as hemicelluloses, gums, and mucilages according to their chemical nature and origin and their d i s tribution i n nature i s very wide since the composition of the polysaccharides may vary considerably i n different parts of any one plant.  Poly-  saccharides are also obtained from seaweed and from certain types of 1  • IT  bacteria and determinations of structure are essential to many branches of science.  The function which they f u l f i l i s not always clear but i t  would appear that the hemicelluloses may act as reserve support structures or reserve food materials depending on their nature and situation in the plant.  They occur i n wood, bark, leaves, and seed pods whilst  the gums are obtained as exudates on the bark of trees or on f r u i t and are used by the plant as a protective mechanism against bacterial invasion or physical damage ( l ) .  The mucilages are of widespread occurence  but are most commonly found i n seeds, where they assist in water storage and may "solubilise" insoluble substances such as cellulose ( 2 ) . Many workers have attempted to define these three classes of polysaccharides.  Generally hemicelluloses are regarded as those polysacc-  harides which are extractable from holocellulose by aqueous a l k a l i . Plant gums are defined as giving a clear solution i n water, whereas mucilages swell but do not dissolve in water.  There are exceptions to  -2this definition since tragacanth gum, vhich i s a tree exudate and a true gum, i s only partly soluble i n vater and behaves as a mucilage (3,4). These polysaccharide materials undergo acid hydrolysis to y i e l d hexoses, pentoses, uronic acids and aldobiouronic acids.  The methyl  pentoses L-rhamnose and L-fucose are also found occasionally and occur in pyranose form as do a l l the other constituents except L-arabinose vhich prefers the furanose ring. have the D-configuration.  The hexoses, uronic acids and xylose  The plant gums a l l contain D-glucuronic acid  except tragacanth gum which contains D-galacturonic acid.  The seed  mucilages on the other hand nearly a l l contain D-galacturonic acid whilst the hemicelluloses shov more variation and may yield  D-gluruconic,  D-galacturonic and 4-0-methyl-D-glucuronic acids whilst 3-0_-methyli  !  glucuronic acid has also been claimed to occur (5) (see l a t e r ) . In the plant gums so far examined D-galactose and L-arabinose are always found whilst D-xylose i s also of very common occurence. Less usual constituents are D-mannose, L-rhamnose, and L-fucose whilst Dglucose has not yet been found.  The mucilages are a more complex family  than the gums and may be c l a s s i f i e d as neutral, acidic, or sulphate ester (seaweeds only).  D-galactose i s universally found and L-arabinose  i s usually present whilst D-mannose, D-glucose, D-fractose and L-rhamnose are less common.  D-xylose i s commonly found i n the acidic mucilages which  contain D-galacturonic acid.  In the hemicellulose family D-xylose i s  very common and xylan-polyuronides  are often present i n woody tissue.  The barks of trees often contain galactan-galacturonides whilst Dgalactose i s also predominant i n leaves and pods and occurs together with L-arabinose i n green non-lignified plant tissues (6).  -3Previous to 1952,  the uronic and aldobiouronic acids were separated  from the hexoses and pentoses by virtue of the i n s o l u b i l i t y of their barium salts in aqueous alcohol.  In that year their absorption from  solution on to weakly basic anion exchange resins was f i r s t u t i l i s e d by Hough, Jones and Wadman (7)  and this i s now the normal method for the  separation of sugar acids from the neutral sugars.  The isolation of  uronic acids from aldobiouronic, aldotriouronic, and acids of higher molecular weight i s best accomplished by partition chromatography on cellulose columns or on sheets of thick paper whilst mixtures of uronic acids may be separated by fractional d i s t i l l a t i o n of their methyl glycoside methyl esters in vacuo. The present work deals with the structure of an aldobiouronic acid isolated from jute hemicellulose.  Structural determinations on aldo-  biouronic acids are of great importance i n studying the chemical nature of polysaccharides  and no comprehensive table of their structures and  sources exists in the l i t e r a t u r e .  Table I i s a literature survey of  this nature giving the structures of the acids known at present.  Table  II comprises those acids whose structure has not been completely determined.  In so far as i t was possible earlier work which has been super-  ceded i s omitted.  In a few cases aldotriouronic acids have also been  isolated and identified.  TABLE I Aldobiouronic Acids of Proved Structure  Structure  2-0-(D-glucuronopyranosyl)D-xylopyranose  Configuration  Source  o<  maize hull hemicellulose  8  oC  oat hull hemicellulose  9  corn cob hemicellulose  10  wheat bran hemicellulose  11  chagual  12  —  3-0-(D-glucuronopyranosyl)D-xylopyranose  4-0-(D-glucuronopyranosyl)D-xylopyranose 4-0-(D-glucuronopyranosy1)D-glucopyranose  2-0-(D-glucuronopyranosy1)D-mannopyranose  sun flower heads  13  cX  wheat straw hemicellulose  14  ex.  pear c e l l wall  15  wheat leaf hemicellulose  16  Kadsura Japonica mucilage  17  oC  corn cob hemicellulose  10  P  Type I I pneumococcus polysaccharide  18  P  Type VIII pneumococcus polysaccharide  19  P  cherry gum  20  damson gum  21  gum ghatti  22  Acacia Karroo gum  23  Neem gum  24  p 1  Acacia Karroo gum  23  egg plum gum  27  p p  wheat straw holocellulose  28  gum arabic  29  black wattle gum  30  Acacia Pycnantha gum  31  —  almond tree gum  32  —  peach tree gum  33  gum ghatti  22  —  P 4-0-(D-glucuronopyranosyl)D-galactopyranose  gum  Reference  —  6-0-(D-glucuronopyranosy1)D-galactopyranose  1  p  - 5 -  TABLE I (cont'd.)  Structure  Configuration  2-0-(4-0-Methyl-D-glucuronopyranosyl)-D-xylopyranose  white b i r c h white elm  4-0-(4—O-Methyl-D-glucuronopyranosyl)-D-galactopyranose  hemicellulose  35  beechwood hemicellulose  37  black spruce h e m i c e l l u l o s e  38  Scots pine  hemicellulose  38  aspen wood h e m i c e l l u l o s e  39  pinus r a d i a t a hemicellulose  40  American beechwood hemicellulose  41  P  L o b l o l l y pine hemicellulose  42  «=><  wheat bran h e m i c e l l u l o s e  11  <X  corn cob  43  ex.  oat h u l l s  oC  cx  hemicellulose hemicellulose  44  birchwood h o l o c e l l u l o s e '  45  s i t k a spruce hemicellulose  46  Pinus r a d i a t a hemicellulose  40  gum  47  myrrh  mesquite  p>  gum  gum  gum  48,49 25,26  gum  myrrh  mesquite  oc  9  flax  grapefruit  4-0-(4-0-Methy1-D-glucuronopyranosyl)-L-arabofuranose  34  36  lemon  6-0-(4-0-Methyl-D-glucuronopyranosyl)-D-galactopyranose  hemicellulose  Reference  western hemlock hemicellulose  oc  3-0-(4-0-Methyl-D-glucuronopyranosylJ-D-xjUJpyranose  Source  25,26 47  gum  48,49  modal  gum  50  lemon  gum  51  -6TABLE I (cont'd.) Structure  Configuration  4-0-(D-galacturonopyranosyl)• • D-xylopyranose  oc  2-0-(D-galacturonopyrano sy 1L-rhamnopyranose  o<  4—0-(D—galacturonopyranosyl)D-galactopyranose  Source  Reference  Plantago arenaria seed mucilage  52  flax seed mucilage  53  Plantago arenaria seed mucilage  54  Plantago ovata seed mucilage  55  okra mucilage  56  slippery elm bark mucilage  57  Karaya gum  58  grape juice sterculia setigera gum  59 60  Karaya gum  58  sterculia setigera gum  61  -7TABLE II Aldobiouronic Acids of Uncertain Structure Structure (D-glucuronopyranosyl)-D-xylopyranose  Source  Reference  Prunus serrulata  62  cottonseed hull hemicellulose  63  (4-0-Methylglucuronopyranosyl)D-xylopyranose  Eucalyptus regnans  64  3-(  cartilage  65  (D-galacturonopyrano sy1)-D-galac t uronic acid  sterculia setigera gum  61  (D-galacturonopyranosyl)-D-galactopyranose  gum jeol  66  (D-galacturonopyranosyl)-D-glucopyranose  asparagus racemosus tuber mucilage  67  cress seed mucilage  68  white mustard seed mucilage  69  cholla gum  70  -D-glucuronopyranosyl)-2-deoxy2-amino-D-galactopyranose  (D-galacturonopyranosyl) -L-rhamnopyranose  -8-  THE IDENTIFICATION OF URONIC ACIDS The characterization of the hexuronic acids and particularly of their monomethyl ethers i s often d i f f i c u l t as their crystalline derivatives are rare and often their preparation i s quite time-consuming. Three main methods are available for this purpose.  Two  involve the  preparation of derivatives from the acid by direct and indirect means, whereas in the third method the acid i s f i r s t reduced to the corresponding neutral hexose from which crystalline derivatives can be more readily obtained. Oxidation of the Uronic Acids In 1931,  Challinor, Haworth and Hirst (29) isolated 2,3,4-tri-0-  methyl-D-glucuronic acid from the hydrolysate of methylated gum  arabic  and proved i t s structure by oxidation with HN0 followed by inethanolysis o o  and d i s t i l l a t i o n to yield the methyl ester of 2,3,4-tri-O-methyl-Dglucaro-1,5-lactone D-glucose.  which was similarly derived from 2,3,4-tri-0_-methyl-  Similar derivatives of methylated uronic acids have been  prepared by many authors following this route.  Edington and Percival  have synthesised 3,4-di-O-methyl-D-galacturonic acid (71) and proved i t s structure by oxidation with bromine water followed by e s t e r i f i c a t i o n to y i e l d the dimethyl ester of 3,4-di-O-methyl-D-galactaric acid.  Haworth,  Hirst, Isherwood and Jones (72) synthesised 2,3,4-tri-O-methyl-Dmannuronic acid which they identified by oxidation with HN0 followed by o  treatment with methanolic ammonia to yield the diamide of 2,3,4-tri-0methyl-D-mannaric acid previously prepared from 2,3,4-tri-0-methyl-Dmannose.  A more unusual proof of structure, was used by White (49)  who  i d e n t i f i e d 4—O-methyl-D-glucuronic acid by periodate oxidation followed  -9by further oxidation with bromine to y i e l d 2-hydroxy-3-methoxy-Lerythrosuccinic acid.  This substance when reacted with a methanolic  solution of methylamine gave the crystalline bismethyl amide. Reduction of the Uronic Acids The reduction of uronic acids with LiAlH^ was f i r s t described by Lythgoe and Trippett (73) and by Abdel-Akher and Smith (74) i n 1950. To confer s o l u b i l i t y i n ether or tetrahydrofuran the methyl ester methyl glycoside of the uronic acid was f i r s t prepared and the f i n a l product was the methyl glycoside of the corresponding hexose.  Since aluminum  salts form stroig complexes with free hydroxyl groups i t i s now usual to isolate the reduced sugar as i t s acetate from which the methyl glycoside of the free sugar i s easily obtained upon saponification.  The reduction  of uronic acids with LiAlH^ works very well and gives good yields of the corresponding neutral sugars from which crystalline derivatives may be made.  This method i s probably the most widely useful means of i d e n t i -  f i c a t i o n of uronic acids known today. Formation of the Amide of the Methyl Glycoside The use of this direct derivative i n characterising uronic acids was f i r s t reported by Smith (75). 4-0-methyl-D-glucuronic  The methyl ester methyl glycoside of  acid obtained from mesquite gum wad d i s t i l l e d  in vacuo and treated with a methanolic ammonia solution.  Evaporation  gave a white solid found to be a mixture of the «*• and /3 forms of the amide and these were easily separated by fractional c r y s t a l l i z a t i o n . This derivative has since been prepared by many authors, the only objection to i t s use being a tedious separation of the <x and p from the o p t i c a l a c t i v i t y of C .  forms arising  -10-  The Identification of Aldobiouronic Acids It i s a well-known fact that the linkage between a uronic acid group and the neighbouring neutral sugar molecule i n a polysaccharide i s peculiarly resistant to acidic hydrolysis.  This i s seen from the  large amounts of aldobiouronic acids produced upon acidic hydrolysis of hemicelluloses, gums and other polysaccharide materials.  The reason for  this resistance i s not yet understood. Due to their widespread occurrence as products of the hydrolysis of polysaccharides the identification of aldobiouronic acids has become of much importance in structural studies.  Unfortunately these materials can  very rarely be characterised directly as scarcely any crystalline derivatives are known.  In a very few cases the amide or methyl ester of a  methyl glycoside has been obtained crystalline (29,53,76,77). Srivastava (78) have obtained the crystalline pentaacetate glucuronopyranosyl)-D-xylopyranose in both i t s ot and  Smith and  of 2-0-(<x-D-  p forms.  This i s  the only occasion on which a xylose containing aldobiouronic acid has yielded a crystalline derivative. It i s an object i n this present work to search for a suitable derivative of the aldobiouronic acid from jute or of a compound easily obtained therefrom. At the present time aldobiouronic acids are identified by reduction to neutral disaccharides followed by hydrolysis and identification of the products.  It i s also essential to determine the points of linkage  of the constituents by methylation of the neutral disaccharide followed by hydrolysis and identification of the methylated fragments.  Such a  long procedure for the characterization of aldobiouronic acids requires a l o t of time and, i f suitable crystalline derivatives were available, t h i s would be greatly reduced.  -11JUTE ALDOBIOURONIC ACID The f i r s t study of jute hemicellulose vas made by Sarkar, Mazumdar and Pal (79) i n 1952.  In i t they determined the optimum conditions for  i t s extraction from holocellulose and carried out detailed analyses of hemicelluloses extracted under varying conditions.  They found the pure  material to contain a monomethyluronic acid and xylose. From methoxy1 content and neutralization equivalent measurements they deduced an equivalent weight of around 1000.  In a further paper based on periodate  oxidation studies on the hemicellulose Das Gupta and Sarkar (80) concluded that jute aldobiouronic acid probably had the structure 4-0-(3T^0methyl-D-glucuronopyranosyl)-^ -D-xylopyranose.  As further evidence  for this structure the same authors i n a letter to the editor (5) told how  they had reduced the methyl ester methyl glycoside with lithium  aluminum hydride and hydrolysed the resulting neutral disaccharide.  The ,  sugars i n the hydrolysate were identified as xylose and 3-0-methyl glucose by paper chromatography in solvent 5. The constituent sugars present in jute oc-cellulose remaining after alkaline extraction of jute holocellulose have been investigated by Adams and Bishop (81).  Formic acid hydrolysis and paper chromato-  graphy of the hydrolysate showed the presence of large quantities of glucose and xylose together with a definite amount of arabinose. may  indicate the occurence of chemical bonding between the  This  oc-cellulose  and the hemicellulose present in jute f i b r e . The Indian workers (80) said that they would present f i n a l evidence for the presence of 3-0-methyl-D—glucuronic acid i n the  hemicellulose  by the preparation and identification of suitable crystalline derivatives.  - 1 2 -  This evidence  has not been produced and furthermore  i t is definitely  shown i n the present work that no d i s t i n c t i o n can be made by paper chromatography between 3-and 4-0-methyl-D-glucose using solvents 1 to 5.*  I f 3-0-methyl-D-glucuronie a c i d r e a l l y i s present  i n the h e m i c e l l u -  l o s e i t i s the f i r s t time i t has been found i n nature whereas methyl-D—glucuronic  a c i d has been found i n many sources  4-0-  (34-46).  Fur-  t h e r i n v e s t i g a t i o n of t h i s question appeared to be d e s i r a b l e . Powdered defatted j u t e was  d e l i g n i f i e d r e a d i l y by means of the  c h l o r i t e process of Wise, Murphy and D'Addieco (81), to y i e l d white h o l o cellulose.  This m a t e r i a l was  extracted with 10$ aqueous sodium  and the s o l u t i o n n e u t r a l i s e d . l o s e was  hydroxide  Upon a d d i t i o n of ethanol the h e m i c e l l u -  thrown out as a f l o c c u l e n t p r e c i p i t a t e .  aqueous a l c o h o l to remove s a l t s the m a t e r i a l was change to give a d i r t y white powder i n 16$  A f t e r washing with d r i e d by solvent  ex-  yield.  A sample of crude hemicellulose was p u r i f i e d by p r e c i p i t a t i o n as in i t s copper s a l t / a l k a l i n e s o l u t i o n . A f t e r c a r e f u l washing the s a l t was decomposed with a l c o h o l i c h y d r o c h l o r i c a c i d and the pure hemicellulose i.  i s o l a t e d as before ( y i e l d 64$). 2.33$, and was 1  The snow-white powder had ash  content  designated hemicellulose I .  Another sample of the crude m a t e r i a l was  suspended f o r a day i n  e t h a n o l i c h y d r o p h l o r i c _ a c i d and the hemicellulose on recovery  was  washed and d r i e d as usual to give a snow-white powder ( y i e l d 70$) an ash content of only 0.28$.  This m a t e r i a l was  designated  with  hemicellu-  lose I I . A comparison of the o p t i c a l r o t a t i o n s , n e u t r a l i s a t i o n equivalents and methoxyl contents of h e m i c e l l u l o s e s I and II showed them to be *  Key  to t h i s i s given on p.  22.  -13-  identical.  P u r i f i c a t i o n as hemicellulose I I was  a b e t t e r product was  t h e r e f o r e adopted as  obtained.  An attempt to e x t r a c t the hemicellulose d i r e c t l y from j u t e without d e l i g n i f i c a t i o n was product  not encouraging.  The y i e l d was  very poor and  the  i s o l a t e d a f t e r p u r i f i c a t i o n by the copper s a l t process had  brown c o l o u r .  a  H y d r o l y s i s of the m a t e r i a l and examination of the hydro-  l y s a t e showed the presence of a t r a c e of glucose which might have derived from c e l l u l o s e present as an  impurity.  T r i a l experiments on the h y d r o l y s i s of j u t e h e m i c e l l u l o s e showed that 1 Normal s u l p h u r i c a c i d f o r s i x to eight hours gave s a t i s f a c t o r y r e s u l t s whereas incomplete  h y d r o l y s i s r e s u l t e d from the use of  formic a c i d even a f t e r twelve hours on the steam bath. of o l i g o s a c c h a r i d e s i n t h i s hydrolysate was  The  45^  presence  demonstrated by f u r t h e r  h y d r o l y s i s with 1 Normal s u l p h u r i c a c i d when chromatography showed only xylose, uronic and aldobiouronic acids to be present.  I t was  not found  p o s s i b l e to avoid the formation of uronic a c i d which occulted also i n the formic a c i d hydrolysate. A large batch of hemicellulose was and the hydrolysate separated t i o n s using Amberlite  IR 120  hydrolysed with s u l p h u r i c a c i d  i n t o n e u t r a l sugar and sugar a c i d f r a c and D u o l i t e A4 r e s i n i o n exchange columns.  Chromatography on these f r a c t i o n s revealed only one n e u t r a l sugar which appeared to be xylose whereas the a c i d f r a c t i o n contained aldobiouronic a c i d s .  L a t e r a second n e u t r a l sugar was  found present  only i n t r a c e amounts and n o t i c a b l e only on h e a v i l y loaded The n e u t r a l sugar was D-xylose. dimethyl  This was  obtained c r y s t a l l i n e and was  confirmed  by the preparation of the  a c e t a l d e r i v a t i v e (82).  The t r a c e sugar was  uronic-and  chromatograms.  identified  as  dibenzylidene identified  only  -14by paper chromatography and ran identically with L-rhamnose i n three solvents. The sugar acid mixture was obtained as a syrup which did not crystallize.  The methyl ester methyl glycoside formed by treatment with  dilute methanolic hydrogen chloride was reduced with lithium aluminum hydride.  The reduced sugar was freed from i t s aluminum complex by  acetylation and the acetate extracted i n chloroform and deacetylated with a l k a l i gave the neutral disaccharide methyl glycoside as a yellow syrup which did not c r y s t a l l i s e .  This syrup was hydrolysed with 1  Normal sulphuric acid as before and the hydrolysate examined chromatographically was found to contain xylose and a monomethyl glucose which might have been 3-or 4-0-methyl-glucose. Attempts to separate the sugars i n the hydrolysate on a cellulose column using solvent 1 were a failure and the separation was carried out on sheets of paper using this solvent.  finally  The sugars were  extracted from the paper i n aqueous acetone and obtained as syrups,one of which crystallized on standing.  This material was identified as D-  xylose and confirmation was again obtained by preparation of the dibenzylidene dimethyl acetal derivatives (82).  The other sugar was shown  to be a monomethyl glucose by demethylation with hydrogen bromide and examination of the product by paper chromatography.  Final and conclu-  sive proof of the position of the methyl group was obtained by preparation of the osazone and arilide.  Comparison of these derivatives against  similar derivatives made from 4-0-methyl-D-glucose revealed that they were identical. It i s worthy of note that 4-0-methyl-D-glucose anilide has not previously been reported i n the l i t e r a t u r e .  This material was  prepared  -15by the standard method for making sugar anilides and the yields vere found to be rather variable since the formation of aniline tars often took place.  The compound gave much d i f f i c u l t y i n recrystallization  from ethyl acetate and the crystals obtained by d i l u t i n g with a few drops of petroleum ether were l i t t l e better.  Eventually a pure product  was obtained after prolonged r e c r y s t a l l i z a t i o n .  The maximum melting  point found was 158-160°C. In a search for -suitable derivatives of 4—O-methyl-B—glucose the dibenzyl mercaptal was also prepared by the method used by Facsu (83) in the preparation of D-glucose dibenzyl mercaptal.  The sugar was con-  densed with oc-toluenethiol i n hydrochloric acid solution i n the presence of zinc chloride.  After addition of water the acid was removed on  Duolite A4 ion exchange resin and the solution evaporated.  The dibenzyl  mercaptal crystallized as a white solid from ethanol and after three recrystallizations from ethanol the white needlelike crystals had a melting point of 158-159°C. llization.  This value did not rise on further crysta-  This derivative has been prepared by an indirect route by  other workers (84,85) and melting points of 73°C. and 96-98°C. have been reported.  I t i s apparent that their materials were not obtained  pure and i t i s possible that the mercaptal was obtained as a hydrate. The dibenzyl mercaptal of standard 3-^0-methyl-D-glucose was also prepared as above.  This compound did not c r y s t a l l i z e from alcoholic  solution but was obtained as white platelets from aqueous alcohol. After two recrystallizations a maximum melting point of 65-70°C. was reached. drate.  The material was apparently not pure and may have been a hyThe compound decomposed on heating i n boiling toluene i n the  Abderhalden i n vacuo i n an attempt to remove water of c r y s t a l l i z a t i o n .  -16-  This was unfortunate as 3-0-methyl-D-glucose dibenzyl mercaptal has never previously been reported. A sample of jute aldobiouronic acid was hydrolysed i n 10$ methano l i c hydrogen chloride for sixteen hours on the steam bath.  After  removal of hydrogen chloride the mixture containing methyl xyloside, uronic acid methyl ester methyl glycoside and the aldobiouronic acid methyl ester methyl glycoside was p a r t i a l l y separated by continuous extraction with ether for twenty-four hours.  The ether layer was shown  to contain methyl xyloside and the uronic acid derivative, whilst the aqueous phase contained a l l three constituents.  The ether extract was  saponified with 0.15 Normal barium hydroxide and the uronic acid methyl glycoside separated by running the solution through Duolite A4 ion exchange resin when the acid remained on the resin whilst the methyl xyloside was removed.  The recovered uronic acid methyl glycoside was  re-esterified with ethereal diazomethane and the amide formed by treatment with methanolic ammonia solution. A mixture of the <x. and of the amide methyl glycoside was obtained on evaporation.  fi forms  The white  solid material was fractionally crystallized from aqueous ethanol solution to y i e l d the pure oc form after four recrystallizations.  This was  shown to be identical to an authentic sample of 4-0-methyl-<x.-D—glucuronamide methyl glycoside (75). A sample of the neutral disaccharide methyl glycoside obtained by reduction of the aldobiouronic acid methyl ester methyl glycoside with lithium aluminum hydride was methylated three times with Haworth's reagents using dimethyl sulphate and 40$ sodium hydroxide solution.  The  partly methylated disaccharide was again methylated using Purdie's reagents v i z . s i l v e r oxide and methyl iodide.  After three such methyl-  -17ations the disaccharide was found to be f u l l y methylated.  Hydrolysis  of the d i s t i l l e d syrup with 1 Normal sulphuric acid for eleven hours was followed by separation of the methylated sugars on sheets of chromatographic paper i n solvent 1. The dimethylxylose obtained as a syrup was oxidized with bromine and on d i s t i l l a t i o n in vacuo white crystalline 3,4-di-0.-methyi-l£-xyl-ono-^-S  -^lactone was obtained.  The tetramethyl glucose was not obtained  pure and the contaminant appeared to be trimethyl rhamnose.  An attempt  to prepare the a n i l i d e o f the tetramethyl glucose was successful but J  the crystalline anilide was not obtained pure due to the smallness of the scale on which i t was made. From this derivative however and paper chromatography i t was almost certain that the tetramethyl  glucose  obtained was 2,3,4,6-tetra-O-methyl-D-glucose. From the evidence presented in this work i t i s concluded that the aldobiouronic acid present in jute must have the structure [A]*  It i s  also evident however that a small amount of a second aldobiouronic acid occurs i n which the neutral sugar unit i s not D-xylose but L-rhamnose. The xylose unit to which the uronic acid i s attached i s part of a chain consisting of mainly xylose units with an occasional rhamnose.  The  length of this chain i s not known but i t i s built up from blocks containing six xylose units to which one uronic acid group i s attached. Jute hemicellulose i s unusual in that i t contains no arabinose. This sugar i s commonly found in hemicelluloses from annual plants.  It  would appear that rhamnose i s involved somewhere i n the biosynthetic pathway's of the jute plant. Whilst this thesis was being written Srivastava and Adams (86) published a short note on work which they had carried out on jute  -18-  hemicellulose.  They also showed the presence of 4-0-methyl-D-glucuro-  n i c a c i d and i d e n t i f i e d the aldobiouronic a c i d as having  s t r u c t u r e [A] .  Their c h a r a c t e r i z a t i o n of the uronic a c i d was based on the preparation of the osazone of the monomethyl glucose In a d d i t i o n they a l s o separated  obtained  as already  described.  an a l d o t r i u r o n i c a c i d i n c r y s t a l l i n e  form and proved i t to be 4-0-methyl-D-glucuronopyranosyl-l,2-oc-D-xylopyranosyl-1,4-|3 -D-xylopyranose.  This shows that the xylose u n i t s i n  the hemicellulose main chain are l i n k e d 1,4. As already mentioned, the jute aldobiouronic a c i d used i n t h i s work contained  appreciable amounts of uronic a c i d formed by h y d r o l y s i s  and also some a l d o t r i u r o n i c a c i d which had not been completely  degraded.  To obtain a pure sample of aldobiouronic a c i d , the crude m a t e r i a l was a p p l i e d as heavy streaks on 3 mm. chromatographic paper and separated by chromatography i n solvent 1.  The pure a c i d was obtained  brown g l a s s with a high p o s i t i v e r o t a t i o n £o<^ ^  as a pale  + 146.5° (CO.75 i n HgO).  This value i s higher than any p r e v i o u s l y reported f o r the m a t e r i a l and it  i s probably  the purest sample y e t prepared. c  Attempts were made to prepare c r y s t a l l i n e d e r i v a t i v e s of t h i s pure a c i d both d i r e c t l y and i n d i r e c t l y . was u n s u c c e s s f u l .  An attempt to prepare the a n i l i d e  A l c o h o l , which i s normally  used as solvent when p r e -  paring sugar a n i l i d e s , could not be used here due to the danger of e s t e r formation.  The a c i d would have had to be d i s s o l v e d i n a p o l a r  solvent and none of s u i t a b l e b o i l i n g point appeared t o be a v a i l a b l e . An attempt to carry out the r e a c t i o n without a solvent f a i l e d as the  j a c i d d i d not appear to d i s s o l v e i n a n i l i n e . In order to overcome the d i f f i c u l t y of e s t e r formation,  a sample  of a l d o b i o u r o n i c a c i d was e s t e r i f i e d with methanolic diazomethane.  -19The methyl e s t e r vas reacted i n methanolic s o l u t i o n v i t h p — n i t r o a n i l i n e . The  l a t t e r d i s s o l v e d on gentle warming but the s o l u t i o n turned brown i n  colour and no p - n i t r o a n i l i d e p r e c i p i t a t e d . was  obtained  On evaporation  a brown syrup  and some unchanged p - n i t r o a n i l i n e .  A f u r t h e r sample of aldobiouronic a c i d was phenylhydrazine i n the same way  allowed  to r e a c t with  as f o r osazone formation.  phous brownish-yellow m a t e r i a l p r e c i p i t a t e d .  This could not have been  an osazone as the 2 - p o s i t i o n on the xylose was the CI of the 4-0-methyl-D-glucuronic a c i d ,  Some amor-  blocked by linkage to  ^he  m a t e r i a l must t h e r e f o r e  have been a phenylhydrazide s a l t or a phenylhydrazone or both.  Attempts  to r e c r y s t a l l i z e t h i s m a t e r i a l f a i l e d and no c r y s t a l l i n e compound obtained  a f t e r separation on an alumina column.  was  I t appeared that the  d e r i v a t i v e d i d not possess a sharp melting point as i t always appeared p l a s t i c i n nature.  H C  OH  H  C  C  H  OH-  0  0  -20-  CHgOX  CO.CgH .N0  2  -C0.CgH .N0  2  4  [C]  [D]  X X =  4  -CO.CHg  y = -H Y = -CH  £  Y = -H  In an attempt t o make a c r y s t a l l i n e d e r i v a t i v e i n d i r e c t l y the a l d o b i o u r o n i c a c i d vas reduced i n a l k a l i n e s o l u t i o n by potassium borofeydride. The off.  r e a c t i o n product vas d i s s o l v e d i n methanol and b o r i c a c i d f i l t e r e d Evaporation  of the s o l u t i o n gave a y e l l o v g l a s s v h i c h was reacted  with excess p-nitrobenzoyl c h l o r i d e i n p y r i d i n e s o l u t i o n *  A f t e r des-  t r o y i n g the excess reagent with sodium bicarbonate, the p-nitrobenzoate was extracted i n t o chloroform and evaporated to y i e l d a golden yellow g l a s s (compound jVj). This m a t e r i a l d i d not c r y s t a l l i s e and was e s t e r i f i e d with e t h e r e a l diazomethane to f a c i l i t a t e i t s separation on an alumina column (compound [cj). Impurities were removed on washing with dry benzene and the e s t e r removed as a pale yellow band on washing with dry benzene c o n t a i n i n g 2fo ethanol.  The product  obtained behaved as a  g l a s s when heated and melted over a very wide range of temperature. I t appeared l i k e l y that the presence of s i x p-nitrobenzoyl groups i n the molecule was s u f f i c i e n t t o prevent  c r y s t a l l i z a t i o n due to t h e i r l a r g e  -21bulk and mutual interference. In a further experiment the x y l i t o l compound obtained as before by borohydride reduction was acetylated with acetic anhydride in the presence of anhydrous sodium acetate.  The acetate was extracted with  chloroform and evaporated to yield a viscous colourless syrup which did not c r y s t a l l i s e on keeping (compound [ D ] ) . No further work was carried out on the aldobiouronic acid.  It  might however have been possible to obtain a crystalline derivative by oxidation with n i t r i c acid for example. successful in the future.  Such an approach may  prove  -22EXPEBIMENTAL Unless otherwise stated a l l paper chromatography was carried out on sheets of Whatman No. 1 chromatography paper.  The developer employed  was p-anisidine reagent and the irrigating, solvents were as follows:1.  ethyl acetate 18,  glacial acetic acid 3,  45$ formic acid 1,  water 4. 2.  1-butanol 40,  95$ ethanol 10,  water 49,  3.  methyl ethyl ketone/water azeotrope.  4.  1-butanol 5,  benzene 1,  5.  1-butanol 4,  glacial acetic acid 1,  pyridine 3,  0.880 ammonia 1.  water 3. water 5,  (upper layer only)  expressed as parts by volume.  A l l evaporations of solvents were carried  out under reduced pressure. The jute used i n this work was purchased from the Beamiss Bag Company of Vancouver. Jute Hemicellulose Jute sacking was cut into strips and reduced to powdered form i n a Wiley m i l l .  Portions of powdered jute (100 gm.) were extracted twice  with 1200 ml. benzene 50/ethanol 50 i n the cold, f i l t e r e d and dried. The dried jute was delignified readily by the method of Wise, Murphy and D'Addieco (81) using sodium chlorite and acetic acid at 70—80°C. for three hours. The white holocellulose obtained was f i l t e r e d off and washed with cold water to give yields of around'90$. Jute holocellulose was extracted overnight i n 1000 ml. 9.3$ aqueous sodium hydroxide and f i l t e r e d .  The remaining solid material was  again extracted with 500 ml. of a l k a l i for several hours and f i l t e r e d  -23-  as before.  The cellulose remnant vas washed well with cold water and  dilute acetic acid, and dried.  The orange-yellow f i l t r a t e s were bulked  and neutralised with glacial acetic acid to give a straw-coloured solution from which the hemicellulose  did not precipitate.  Upon addition  of two volumes of ethanol jute hemicellulose was thrown out as a curdy precipitate and was  isolated by centrifugation.  The product was washed  several times with 5 0 $ ethanol to remove inorganic salts, then with i n creasing strengths of alcohol and f i n a l l y dried by solvent exchange to yield a white powder ( 1 6 gm. from 1 0 0 gm. jute). Purification of Jute Hemicellulose Crude hemicellulose  ( 5 gm.)  was dissolved in 3 0 ml. 10fe aqueous  sodium hydroxide and 5 0 ml. Fehling's solution added. precipitate was  The greenish-blue  l e f t standing overnight and isolated by centrifugation.  After careful washing with alcoholic sodium hydroxide followed by washing with ethanol, the complex was decomposed with dilute ethanolic hydrogen chloride and washed free of chloride ion with aqueous ethanol before isolation as a white powder by solvent exchange. cellulose I ,  gm.)  3.2  had ash content  2.33$,  [°°]  This material (hemi^  ~  45.1°  (calculated  as ash free C. 0 . 1 5 in 2 N NaOH). N . E . of 9 5 3 indicated 2 1 . 7 $ anhydrouronic acid units. A second batch of crude hemicellulose  ( 5 gm.)  ml. ethanol containing 4 . 5 ml. hydrogen chloride. night the suspension was  suspended i n 1 5 0  After standing over-  centrifuged and the precipitate washed free  of chloride ion as before. was  was  After solvent exchange the  hemicellulose  obtained as a snow-white powder (hemicellulose I I , 3 . 5 gm.)  ash content indicated  0.28$  20.6$  and  [oc]  ^°  -  47.1°  (C.  0.5  anhydrouronic acid units.  in  2N  NaOH).  N.E.  with of  The methoxyl content of  1005  -243.18$  indicated a mean E. Wt. of 975 or 21.3$  anhydrouronic acid.  An attempt to prepare absolutely pure hemicellulose by electrodialysis of an aqueous solution of the crude material f a i l e d as the pure material vas precipitated in gel form from vhich i t vas found impossible to remove the last traces of vater by solvent exchange. In viev of the higher purity obtained, the main batch of jute hemicellulose vas purified by the ethanolic hydrogen chloride method and vas obtained as hemicellulose I I . Attempted Direct Extraction of Hemicellulose from Jute A 100 gm. sample of jute vas solvent extracted and then a l k a l i extracted i n the usual vay.  The hemicellulose vas purified by the  copper salt method to yield a brovnish-vhite powder (4.9 gm.). tent 6.38$,  ~ 47.0° (calculated as ash free C. 1.25  A sample (304 mg.)  Ash con-  in 2N NaOH).  of this material vas hydrolysed on the steam  bath for, sixteen hours v i t h 1 Normal sulphuric acid and the hydrolysate  i neutralised v i t h barium carbonate, the solution obtained being deionised in an Amberlite IR 120. resin column.  The concentrated eluate shoved  chromatographic spots corresponding to xylose, glucose, uronic acid, aldobiouronic acid, and oligosaccharides vhen irrigated in solvents 1 and 2 and developed v i t h p-anisidine spray reagent.  The glucose vas  present only in trace amounts. Jute Aldobiouronic Acid In a preliminary experiment hemicellulose II (2 gm.)  vas hydrolysed  v i t h 30 ml. 1 Normal sulphuric acid for six hours on the steam bath and the acids neutralised v i t h barium carbonate.  The hydrolysate vas  deionised i n an Amberlite IR 120 resin column and the  concentrated  -25eluate shoved spots with Rx values 0.30, 0.69, 1.00 and 1.44 corresponding to oligosaccharide, aldobiouronic acid, xylose, and uronic acid when chromatographed i n solvent 1. Another t r i a l hydrolysis of hemicellulose II (3 gm.) vas carried out i n 100 ml. 45$ formic acid.  After twelve hours on the steam bath  the formic acid vas removed by evaporation under reduced pressure. Chromatography shoved the same spots as before with a larger amount of aldotriuronic acid (Rx 0.35) apparently due to incomplete hydrolysis. Further hydrolysis of the material i n 1 Normal sulphuric acid removed this spot v i t h a corresponding increase i n uronic and aldobiouronic acid. A large batch of hemicellulose II (15.0 gm. expressed as dry weight) was hydrolysed on the steam bath i n 400 ml. 1 Normal sulphuric acid and the reaction followed on the polarimeter.  After seven hours the rota-  tion had reached a steady valie of +57° when the acids were neutralised with barium carbonate as before and deionised i n an Amberlite IR 120 resin column.  Upon running the eluate through a Duolite A4 resin column  the sugar acids were retained and the neutral sugar fraction obtained in solution.  The column was carefully washed with water and the sugar  acids eluted with 1 Normal sodium hydroxide.  Upon returning this eluate  to the Amberlite IR 120 column a solution of the sugar acids was obtained. The neutral sugar solution when concentrated under reduced pressure yielded a pale yellow syrup (9.976 gm.) which crystallised overnight. It appeared at f i r s t to contain only xylose when spots were irrigated in solvent 1 but later a true sugar with an Rx value greater than that of xylose was found. The sugar acid fraction when concentrated under reduced pressure  -26gave a yellow glass (3.604 gm.). Spots of this material when irrigated in solvent 1 showed the presence of an appreciable amount of uronic acid and small amounts of triuronic acid besides the main fraction of aldobiouronic acid. i t i s 9.1^)  The fraction had OMe 8.05$ (calculated for J ° + 124.4° (C. 0.5 i n H 0).  CjgHggOjj i t i s 340).  2  C.QH^O,,  N.E. 314 (calculated for  The low values of the inethoxyl vaue and neutral-  isation equivalent were attributable to the uronic acid present i n the fraction. The recovery of sugars from the hydrolysate was approximately 90$ and the anhydrouronic  acid content of 18$ was i n f a i r agreement with  the value estimated by other methods. Identification of Neutral Sugars The crystallised neutral sugar fraction was twice recrystallised from methanol to give white prismatic crystals melting point and mixed melting point 143-145°C. with an authentic sample of pure xylose, ^cx-Jjg,^ + 17.0° (equivalent C. 1.0 i n HgO). The dibenzylidene dimethyl acetal derivative was prepared by d i s solving a sample of the sugar (686 mg.) i n 7 c c . of benzaldehyde methanolic hydrogen chloride reagent (82).  This reagent was prepared  by dissolving freshly d i s t i l l e d benzaldehyde (40 ml.) i n a mixture of methanolic hydrogen chloride (20 ml., 2.5N) and methanol (120 ml.). After standing for four days a white crystalline product was obtained. Two recrystallizations from methanol/benzene gave fine white needlelike crystals melting point and mixed melting point 211°C. with a standard derivative made from crystalline  D—xylose.  A sample of the true sugar was obtained when a sheet of Whatman  -273 mm.  chromatographic paper vas heavily streaked v i t h the neutral sugar  mixture and irrigated in solvent 1.  The band of sugar vas  extracted  into 80$ aqueous methanol and concentrated to give a yellov syrup. Chromatography in solvents 1, 3 and 4 against standard rhamnose and  xylose  shoved that the unknown sugar vas L—rhamnose. Reduction of Jute Aldobiouronic  Acid  The aldobiouronic acid (2.210 gm.)  vas treated v i t h 3$ methanolic  hydrogen chloride on a steam bath under reflux and the reaction followed on the polarimeter. attained.  After five hours a constant rotation of +112°  vas  The hydrogen chloride vas neutralised with lead carbonate  and the precipitate removed after centrifugation.  After careful washing  of the precipitate with methanol the f i l t r a t e and washings were bulked and evaporated to yield the methyl glycoside methyl ester (2.697  gm.)  as a thin brown syrup. Finely crushed lithium aluminum hydride (2.8 gm.) 120 ml. dry tetrahydrofuran  was  suspended in  and refluxed to promote dispersion.  A solu-  tion of the methyl ester methyl glycoside of the aldobiouronic acid in 50 ml. dry tetrahydrofuran was added gradually to the cooled suspension and the reaction mixture refluxed for t h i r t y minutes.  Excess reagent  was destroyed by the addition of ethereal ethyl acetate solution and the solvents removed under reduced pressure. and anhydrous sodium acetate (3.5 gm.)  Acetic anhydride (50  ml.)  was added to the reaction vessel  which was heated under reflux for three hours on the steam bath.  After  evaporating off excess acetic anhydride the inorganic salts were dissolved i n dilute hydrogen chloride and the solution extracted with 250 ml. chloroform in four separate washings.  The chloroform extract  was  -28freed of chloride ion by washing with water and the solvent removed to give a mobile yellow syrup of the disaccharide methyl glycoside pentaacetate(3.68  gm.).  Removal of the acetjl groups was accomplished by saponification in 20 ml. ethanol with 20 ml. 1 Normal sodium hydroxide for one hour on the steam bath.  After deionising in Amberlite IR 120 followed by Duolite  A4 resin columns the solution of the disaccharide methyl glycoside was evaporated to give a viscous yellow syrup (2.093 gm.). (calc. for C H 4 i o 0  13  2  i s  18  * #)> 2  M  D°'  +9 8 , 5  ° (* C  0 , 7 5  i n  OMe H  19.7$  2 ^* fl  Hydrolysis of the Neutral Disaccharide. The disaccharide methyl glycoside (850 mg.) was hydrolysed i n 50 ml. 1 Normal sulphuric acid on the steam bath and the reaction followed on the polarimeter.  After fourteen hours a steady rotation of +44.5°  was attained. The hydrolysate was neutralised with barium carbonate and the precipitate removed by centrifugation and washed free of carbohydrate material. The f i l t r a t e and washings were bulked and evaporated to y i e l d a viscous yellow syrup (820  mg.).  Paper chromatograms were spotted with this material and irrigated in solvents 1, 2, 3, 4 and 5 using D-xylose, 3-0-methyl-D-glucose, and 4-0-methyl-D-glucose as standards.  An excellent separation was achieved  in solvent 1 giving two spots Rx 0.98 and 1.24.  There was no doubt  that the slower yellow spot was xylose but the faster pale brown spot might have been either 3-or 4-0-methyl-D-glucose.  These sugars were  found to be quite impossible to distinguish chromatographically. Separation of the Sugars in the Hydrolysate Attempts to separate the monomethyl glucose from the xylose using  -29a cellulose column irrigated with solvent 1 were unsuccessful and only a p a r t i a l separation was achieved.  The sugar mixture (500 mg.) was  streaked on sheets of Whatman 3 mm. prewashed chromatographic  paper and  irrigated for sixteen'hours i n solvent 1. After drying the sheets the sugar zones were located by spraying strips with p-anisidine reagent. A good separation was achieved and the sugars were extracted from the paper into 80$ aqueous methanol.  Evaporation of the extracts yielded  two chromatography cally pure sugars.  One fraction (120 mg.) had Rx 0.98  in solvent 1 and was apparently D-xylose whilst the other (200 mg.) had Rx 1.23 and was the monomethyl glucose* Identification of D-xylose The extracted sugar crystallised on standing for two days and after treatment with charcoal i n aqueous solution and evaporation i t was obtained as white prismatic crystals j ^ - J ^ 22.9° (equil. Literature +  value + 18.0°).  The dibenzylidene dimethyl acetal was made as already  described (82) and after recrystallization from benzene/petroleum ether was obtained in the form of white needles melting point amd mixed melting point 211°C. with a standard derivative made from crystalline Dxylose. Identification of L-rhamnose When attempting the separation of xylose and monomethyl glucose on a cellulose column three tubes were obtained containing a sugar running faster than monomethyl glucose i n solvent 1. This appeared to be present in only trace amounts and i t s identification was only carried out by paper chromatography.  When examined i n solvents 1, 2 and 4 the unknown  had Rx values of 1.58, 1.88 and 1.23 respectively and ran side by side  -30with a standard spot of L-rhamnose.  Both sugars gave a pale yellow  spot with p-anisidine reagent. Identification of 4 Methyl Glucose (a) Demethylation A sample of the chromatographically pure sugar (20 mg.) was heated with 1.5 ml. 40$ hydrobromic acid i n a sealed tube i n the steam bath for five minutes when the solution i n the tube was diluted with 20 ml. water.  The hydrobromic acid was removed on Duolite A4 exchange resin  and the deionised solution evaporated to give a pale yellow syrup.  When  examined by paper chromatography i n solvent 4 this syrup showed spots coinciding with B—glucose and unreacted monomethyl glucose. (b) Preparation of the osazone A portion of monomethyl glucose (55 mg.) was dissolved i n 1.8 ml. water and 0.18 ml. freshly d i s t i l l e d phenylhydrazine, 12. ml. 20$ acetic acid and 60 mg. sodium bisulphite added.  The reaction was carried out  in a water bath aat 70-80°C. for two hours when the osazone separated as small yellow crystals which were f i l t e r e d off and recrystallized twice from aqueous alcohol to y i e l d small yellow needlelike crystals of the osazone melting point 159-160°C. without  decomposition.  The osazones of standard 3-and 4-0-methyl-D-glucose were prepared in similar fashion. 4—0-methyl-D-glucosazone was obtained as small golden needles from aqueous alcohol melting point 158.159°C. (84) but the 3-methyl analogue (yellow sheaves) did not give a sharp melting point even after many recrystallizations from aqueous alcohol and aqueous acetone.  The best value obtained was 168-172 C. (values of 164-  166°C. (87) and 178-179°C. (88) are reported i n the l i t e r a t u r e ) .  -31The osazone from jute gave mixed melting point 158-159°C. v i t h 4-0-methyl-D-glucosazone and 146-164°C. with 3-0-methyl—D-glucosazone. (c) Preparation  of the anilide  To a sample of monomethyl glucose (99 mg.)  was  added 2 ml.  absol-  ute alcohol and 0.1 ml. freshly d i s t i l l e d dry aniline. After refluxing on the steam bath for one and a half hours the reaction was  stopped and  the alcohol and excess aniline removed by evaporation i n vacuo.  The  i  pale brown reaction product was treated with 20 ml. ethyl acetate under reflux and the extract upon concentration  yielded pale yellow crystals  of the a n i l i d e . After three recrystallizations from ethyl acetate small white needlelike crystals were obtained (15 mg.) 158-160°C.  melting point  Further recrystallization did not raise this value.  A sample of 4-0-methyl-D-glucose anilide was from the standard sugar.  similarly prepared  It yielded white mushroom l i k e crystals melt-  ing point 156-158°C. from straight ethyl acetate solution.  This material  was d i f f i c u l t to obtain pure and the melting point quoted was the highest that could be obtained. The mixed melting point for these derivatives' was (d) Preparation  156-159°C.  of other standard derivatives  In a search for suitable derivatives of standard 3-and 4-0-methylD-glucose the dibenzyl mercaptals were prepared. Standard 4-0-methyl-D-glucose (270 mg.) hydrogen chloride and 0.33  was  dissolved i n 0.35  ml.°<- toluenethiol and 150 mg.  zinc chloride added to the solution.  granular  After placing in the mechanical  shaker for six hours a one phase liquid was  obtained, and this was  uted with water throwing out a white o i l from solution. chloride was  ml.  removed on Duolite A4 resin which was  dil-  The hydrogen  f i l t e r e d off and  -32washed with alcohol.  The f i l t r a t e and washings were bulked and evapor-  ated to yield a thick yellow o i l which s o l i d i f i e d overnight. dissolved i n absolute alcohol and treated with charcoal.  This was  After f i l t r a -  tion and concentration of the f i l t r a t e white crystals of the mercaptal were obtained (50 mg.).  These after three recrystallizations from ab-  solute alcohol had melting point 158-159°C.  Further r e c r y s t a l l i z a t i o n  did not raise this value. An attempt was made to prepare 3-0-methyl-D-glucose dibenzyl mercaptal i n similar fashion.  The material could not be induced to crys-  t a l l i z e from absolute alcohol but a crop of white platelike crystals was obtained after diluting the concentrated alcoholic solution with a few drops of water.  These had melting point 06-69°C. before and after  recrystallization from aqueous alcohol.  Upon drying this material in  the Abderhalden over boiling toluene decomposition took place and a small amount of yellow o i l remained. Methanolysis of Jute Aldobiouronic Acid A sample of aldobiouronic acid (3.06 gm.)  was treated with 10$  methanolic hydrogen chloride on the steam bath overnight.  After neut-  ralization with lead carbonate and evaporation of the f i l t r a t e a dark brown syrup (3.07 gm.)  was obtained.  This showed three spots when  chromatographed i n solvent 2 the Rx values being 0.23,  1.00 and  2.11.  The mixture was continuously extracted into ether for one day and the ethereal and aqueous phases evaporated to jield brown syrups (0.979 gm. and 1.544  gm. respectively).  The syrup from the aqueous phase was dissolved i n 50 ml. 0.15 Normal barium hydroxide and kept at 60°C. for two hours when the excess a l k a l i  -33was destroyed by the addition of solid carbon dioxide.  The precipi-  tated barium carbonate was centrifuged off and the f i l t r a t e deionised with Amberlite IR 120 resin.  When the eluate was run through Duolite  A4 resin a solution of methyl xyloside was obtained.  The acids were  eluted from the column i n 30 ml. 1 Normal sodium hydroxide and this on running through Amberlite IR 120 resin yielded a solution of the acid component which on evaporation gave a brown syrup (0.643 gm.).  Chroma-  tography in solvent 1 and spraying with a 1$ bromophenol blue indicator solution showed two yellow spots with Rx 0.18  and 0.49  due to aldobio-  uronic and uronic acid methyl glycosides. A similar treatment of the ether extracted syrup gave an acid component (0.431 gm.)  Rx 0.53  corresponding  to the methyl glycoside of the  uronic acid. The methyl xyloside solutions were bulked and evaporated to y i e l d a pale yellow syrup (0.687 gm.)  which gave fernlike crystals on keeping. f  This material was not further investigated. Characterisation of Jute Uronic Acid The uronic methyl glycoside (431 mg.)  obtained above was  f i e d with ethereal diazomethane and evaporated.  esteri-  The methyl ester  methyl glycoside was dissolved in 25 ml. cold saturated methanolic ammonia and allowed to stand for two days.  Evaporation gave a white  s o l i d which was decolourised with charcoal in methanol solution. Concentration yielded white mushroomlike crystals melting point 204-213°C. After four recrystallizations from aqueous ethanol small white p r i s matic crystals of 4-0-methyl-oc-D—glucuronamide methyl glycoside were obtained melting point and mixed melting point 234.5-236°C. with a standard sample.  (Literature value 236°C. (75)).  -34Methylation of Neutral Disaccharide To the neutral disaccharide methyl glycoside (864 mg.) vas added 6 ml. 40$ sodium hydroxide solution followed by 0.5 ml. dimethyl s u l phate.  The mixture vas stirred at high speed at a temperature  of 45-  55°C. and 0.5 ml. portions of dimethyl sulphate added every f i f t e e n minutes for one and a half hours.  A further addition of 6 ml. 40$  sodium hydroxide vas then made and the vhole cycle of operations repeated twice so that the total reaction time was four and a half hours. The whole procedure was repeated twice more so that i n a l l nine 6 ml. portions of 40$ sodium hydroxide and 27 ml. dimethyl sulphate were used.  The excess dimethyl sulphate was destroyed at the end on  heating the mixture to 80°C. for half an hour.  After neutralisation to  pH 8.9 with sulphuric acid the reaction mixture was continuously extracted with chloroform overnight.  Evaporation of the extract gave a  yellow mobile syrup (675 mg.) whose infra-red spectrum showed only a weak hydroxyl function. The partly methylated syrup was dissolved i n 20 ml. dry methyl iodide and a few grains of Drierite added.  Silver oxide (5 gm.) was  added i n small amounts to the reaction mixture.kept at 50°C. under reflux i n a flask f i t t e d with mercury sealed s t i r r e r .  After nine hours  acetone was added and the excess methyl iodide d i s t i l l e d o f f . The methylated sugar was f i l t e r e d i n acetone solution and the f i l t r a t e returned to the flask for evaporation of the solvent. After three such methylations the product gave an infra-red spectrum showing zero hydroxyl function.  The methylated sugar was purified by d i s t i l l a t i o n i h  vacuo when a pale yellow syrup (517 mg.) was obtained (bath temperature 170-180OC. at 0.01 mm. Hg). Oide content 55.7$ (calculated f o r  -35C  18 34°10 H  1 8  6 2  » ^)[ 9  £ X  ] 1° + 108.6° (C. 1.75 i n CBClg).  The high  methpoxyl content found was due to the presence of some rhamnose containing disaccharide present as impurity. Hydrolysis of Methylated Disaccharide and Separation of the Methylated Sugars The methylated disaccharide (437 mg.) was dissolved i n 25 ml. 1 Normal sulphuric acid and hydrolysed oh the steam bath for eleven hours when a steady rotation of +81.0° was attained.  The acid was neutralised  with barium carbonate and the precipitate centrifuged off and washed free of carbohydrate.  The f i l t r a t e and washings were bulked and evapor-  ated to y i e l d a yellow syrup (396 mg.) showing two spots R '0.68 and 0.83 when chromatographed i n solvent 1. 1  The spots gave buff and pale  yellow colours with p-anisidine reagent, the former resembling  3,4-di-  methyl xylose whilst the latter ran identically to 2,3,4,6-tetramethyl glucose i n solvents 1 and 2. The mixture of methylated  sugars (396 mg.) was streaked on pre-  washed Whatman 3 mm. chromatographic paper and irrigated i n solvent 1. The zones were located by spraying strips and the sugars were extracted from the dried paper using ether for the tetramethyl glucose and absolute alcohol for the dimethyl,xylose.  Evaporation of the extracts  gave syrups of tetramethyl glucose (129 mg.) and dimethyl xylose (56 mg.). Identification of 2,3, 4 6-tetra-0-methyl-D-glucose :  >  The extracted sugar showed traces of trimethyl rhamnose as impurity when examined on chromatograms.  Attempts to c r y s t a l l i s e the tetra-  methyl glucose from ether solution were unsuccessful and an attempted fractional d i s t i l l a t i o n of the syrup i n vacuo did not y i e l d a pure  -36product.  Finally a second separation on paper yielded some pure t e t r a -  methyl glucose (26 mg.). The anilide was prepared i n the usual way and a few long needlelike crystals were obtained.  The material was recrystallised from  absolute alcohol and gave melting point 122-132°C. (literature value 138°C. (89)). Owing to the smallness of the sample i t was impossible to recrystallize the material to constant melting point.  The mixed  melting point' with standard 2,3,4,6-tetra-0-methyl-D-glucose was 130-136°C. Identification of  anilide  J  3.4-di-0-methyl-D-xylose  The dimethyl xylose (56 mg.) was dissolved i n 2 ml. water and 20 drops bromine added.  The well-stoppered flask was kept for two days  in the dark when a spot on paper gave a negative test with p-anisidine spray.  The bromine was removed by aeration and" hydrobromic acid  neutralised with s i l v e r oxide.  After centrifugation and washing of  the precipitate the bulked f i l t r a t e and washings were treated with hydrogen sulphide for three minutes.  After evaporation the product  was taken up i n a l i t t l e water, centrifuged and transferred to a clean flask.  Evaporation yielded a pale brown glass (47 mg.) and on d i s t i l -  lation i n vacuo white needlelike crystals were obtained (bath temperature 140-160°C. at 0.1 mm. Hg). The lactone (25 mg.) had melting point 58-64°C. and was contaminated with a small amount of colourless syrup. R e d i s t i l l a t i o n gave crystals of 3,4-di-0-methyl-D-xylosemelting point 64-66°c. (literature value 64-66°C. (8)).  &-lactone  -37Pure Jute Aldobiouronic Acid Impure aldobiouronic acid (4.65 gm.) prepared i n the usual way was heavily streaked on Whatman 3 mm. chromatographic paper at a load of approximately  8 mg. per cm. After i r r i g a t i o n i n solvent 1 for six-  teen hours the aldobiouronic acid was located by the method of spraying strips.  The dried paper was extracted with 80$ aqueous acetone u n t i l  a faint Molisch test was given by the extract. chromatographically  On evaporation the  pure aldobiouronic acid was obtained as a brownish-  white glass (0.947 gm.) [ot] ^  + 146.5° (C. 0.75 i n HgO).  The uronic' acid zone was also retained and extracted with 80$ aqueous acetone to y i e l d on evaporation a brownish-yellow glass (0.124 gm.).  The material was found to be chromaiographically pure^exJ ^ +  55.0° ~(C. 1.25 in HgO). Attempted Preparation of a Crystalline Derivative by Direct Methods An attempt to make the anilide from the aldobiouronic acid was unsuccessful since the choice of solvent gave d i f f i c u l t y .  The acid did  not react with aniline without a solvent being present. A sample of aldobiouronic acid (82 mg.) was e s t e r i f i e d with methano l i c diazomethane and evaporated to give a brown syrup.  Upon reaction  with recrystallized p-nitroaniline (45 mg.) i n methanol (2 ml.) a dark brown solution was obtained after heating at 70°C. for fifteen minutes. No crystalline p-nitroanilide was found and when the solution was d i l uted with water some p-nitroaniline was recovered unchanged. A further portion of acid (71 mg.) was dissolved i n 2 ml. water o and reacted at 80 C. with 0.13 ml. d i s t i l l e d phenylhydrazine  i n the  presence of 20$ acetic acid (1.4 ml.) and sodium bisulphite (50 mg.).  38After three hours the mixture was allowed to cool when a yellow-brown solid separated.  This material was f i l t e r e d off and applied to the top  of an alumina column after dissolving i n the minimum volume of acetone. Excess phenylhydrazine was removed by washing with benzene containing 2$ ethanol.  The derivative remained as a brown band at the top of the  column and was f i n a l l y removed i n 5$ aqueous alcohol solution.  After  treatment with charcoal, f i l t r a t i o n and evaporation the material was recrystallised from aqueous alcohol and had melting point 95° to 130°. The indefinite melting point persisted after a further recrystallization and the attempt to obtain a satisfactory crystalline derivative by this method was abandoned. Attempted Preparation of a Crystalline Derivative by Indirect Methods A sample of acid (107 mg.) was dissolved i n 2.0 ml. water and made alkaline by the addition of 1.0 ml. 5 Normal sodium hydroxide. the addition of potassium borohydride (55 mg.)  After  the reduction was allowed  to proceed i n the cold for two hours when the excess reagent was destroyed with glacial acetic acid.  The solution was deionised with Amber-  l i t e IR 120 exchange resin and f i l t e r e d .  Evaporation gave a mixture of  the x y l i t o l compound with white crystalline boric acid.  This mixture  was acetylated with acetic anhydride (5 ml.) i n the presence of anhydrous sodium acetate (150 mg.)  under reflux on the steam bath.  After three  hours the excess acetic anhydride was d i s t i l l e d off under reduced  pres-  sure and the inorganic salts dissolved i n dilute hydrochloric acid. The solution was extracted three times with chloroform and the bulked extracts washed free of chloride ion with water.  Evaporation yielded  a pale yellow viscous syrup (41 mg. Compound [©])• c r y s t a l l i z e the acetate were unsuccessful.  A l l attempts to  -39A large batch of acid (655 mg.) was reduced with potassium  boro-  hydride as before and the x y l i t o l compound dissolved i n acetone.  The  boric acid was f i l t e r e d off and the solution evaporated to yield a yellow glass (623 mg. 1 mole).  This was dissolved i n dry pyridine  (40 ml.) and reacted with 4.23 gm. (12 moles) pure p-nitrobenzoyl chloride on the steam bath under reflux for two hours.  After standing  overnight a heavy precipitate probably of pyridine hydrochloride was obtained.  Excess saturated sodium bicarbonate solution was added to  the reaction mixture until no further effervescence was observed and the solution l e f t for three hours.  The solution was extracted three  times with chloroform and the chloroform extracts washed free of b i carbonate with water.  Evaporation of the extract yielded a yellow  glass (1.265 gm. Compound [&])• Only a fraction (800 mg.) of this material was soluble i n chloroform the remainder having been dissolved by pyridine which had carried over i n the chloroform extract. This fraction was dissolved i n chloroform and methylated with ethereal diazomethane.  Evaporation gave the  p-nitrobenzoate methyl ester as a golden yellow glass (800 mg. Compound [c]).  A sample of this compound (158 mg.) was applied to the top of  an alumina column i n chloroform solution (3 ml.) and the column i r r i gated with 400 ml. dry benzene.  This was followed by i r r i g a t i o n with  dry benzene containing 2$ ethanol when the p-nitrobenzoate came off as a thin yellow band.  When evaporated this gave a yellow material (69  mg.) melting point 97 to 185°C. which was apparently a glass.  The ben-  zene extract yielded a mixture of p-nitrobenzoate and what appeared to be methyl p-nitrobenzoate present as an impurity melting point 75-80°C. It did not appear that the p-nitrobenzoate of the x y l i t o l compound could be obtained c r y s t a l l i n e .  -40BIBLIOGRAPHY 1.  White, E.V., Tappi Monograph No. 6 . (1948).  2.  Kirchaner, W. and Tollens, B., Ann., 17JT : 205 (1874~).  3.  O'Sullivan, C , J . Chem. S o c , 1164 (1901).  4.  James, S.P. and Smith, F., J . Chem. S o c , 739 (1945).  5.  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