RODD'S CHEMISTRY

OF CARBON COMPOUND S

A modern comprehensive treatise

SECOND EDITIO N

Edited by

S . COFFE YM.Sc. (London), D.Sc . (Leyden), F.R.I .C.

formerly ofI.C.I . Dyestuffs Division, Blackley, Mancheste r

VOLUME I PART F

PENTA- AND HIGHER POLYHYDRIC ALCOHOL S

THEIR OXIDATION PRODUCTS AND DERIVATIVE S

SACCHARIDES

CONTRIBUTORS TO THIS VOLUM E

Professor G . O . ASPIN ALL, D .SC ., PH .D ., F.R.S.E ., F .R .I .C .

Department of Chemistry, Trent University, Peterborough, Ontario, Canad a

Professor L . HOUGH, M .SC ., PH .D . (MANC .), D .SC . (BRISTOL )

Department of Chemistry, Queen Elizabeth College, Kensington, London, W . 8

(Mrs .) E . E . PERCIVAL, B .SC . (BIRM .), PH .D ., D .SC . (EDIN .), A.R.I .C .

Department of Chemistry, Royal Holloway College, Egham, Surre y

D . A . REEs, B .SC ., PH .D . (WALES)

Department of Chemistry, The University, Edinburgh, 9

(MTS .) M. RENNIE, B .SC ., PH .D .

Department of Chemistry, The University, Edinburgh, 9

A . C. RICHARDSON, B .SC ., PH .D . (BRISTOL)

Department of Chemistry, Queen Elizabeth College, Kensington, London, W . 8

R . E . FAIRBAIRN, B .SC ., PH .D ., F .R .I .C .

formerly of I .C .I . Dyestuffs Division, Research Department, I .C.I . Ltd . ,

Blackley, Manchester 9 (Index )

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PREFACE VI I

OFFICIAL PUBLICATIONS XI VSCIENTIFIC JOURNALS AND PERIODICALS XI V

LIST OF COMMON ABBREVIATIONS AND SYMBOLS USED XV'

Chapter 22 . Penta-, Hexa- and Higher Polyhydric Alcohols

L . HOUGH and A . C. RICHARDSON

i . General introduction ia. Nomenclature, stereochemistry and structural representation

ib. Preparation and synthesis of alditols 1 1

c. Chromatographic separation of alditols 1 4z . Individual alditols i 8

a. Pentitols 1 8b. Hexitols 1 9c. Heptitols and higher alditols 2 4

3 . Reactions and derivatives of the alditols 2 5a. Oxidation 2 5b. Cyclic acetal and ketal formation 3 2c. Esterification

3 8(i) With organic acids, 38 - (ii) With inorganic acids, 40 - (iii) Complexingwith polybasic acids, 4 1

d Etherification

4 5(i) Methyl ethers, 45 - (ii) 2,4-Dinitrophenyl ethers, 4 5

4 . Monoanhydroalditols 4 65 . Dianhydroalditols 5 16 . Deoxyalditols 557 . Aminodeoxyalditols 5 88 . Deoxynitroalditols 6 1g . Sulphur-containing derivatives of the alditols 64

Chapter 23 . The Monosaccharides : Pentoses, Hexoses ,Heptoses and Higher Sugars

L. HOUGH and A. C . RICHARDSO N

1 . Monosaccharides 67-a. Nomenclature, structure and stereochemistry

68,(i) Early history, 68 - (ii) The Fischer and Fischer-Kiliani syntheses ; linearstcreochcmical formulae, 70 - (iii) Furanose and pyranose structures ;anomeric forms, 74 -- (iv) Equilibration ; isolation of individual isomers,78 - (v) Glycosides and methylated derivatives, 79 - (vi) Oxidation : theMalaprade periodate and Criegee reactions, 8 3

b. Conformational analysis of the monosaccharides

8 7(i) The pyranose ring ; chair conformations, 87 - (ii) Boat and skew con-formations, 91 - (iii) Instability factors and preferred conformations, 95 -(iv) Conformation and chemical effects, too - (v) Equilibration in solution ;mutarotation ; complex formation, 104 - (vi) Furanoid rings, 112 - (vii)Stereo-electronic factors in displacement and esterification reactions, 118

c . Identification and structural determination of monosaccharides b yphysical methods 12 4(i) Crystal structure analysis, 124 - (ii) Infrared spectroscopy, 127 - (iii )Mass spectrometry, 133 - (iv) Nuclear magnetic resonance, 139 - (v) Optica lrotatory power and molecular disymmetry, 16 4

d .* Separation, identification and estimation of monosaccharides bychromatography and related techniques 1 7 5(i) Paper chromatography, 176 - (ii) Paper electrophoresis, 181 - (iii) Thin -layer chromatography, 185 - (iv) Gas-liquid chromatography, 189 - (v)Column chromatography, 1 93

e. Synthesis of monosaccharides

19 8(i) Total synthesis, 198 - (ii) Ascent of the series, 203 - (iii) Descent of th eseries, 211 - (iv) Changes in configuration at asymmetric carbon atoms ,220 - (v) Oxidation of alditols, 22 7

f. Natural sources, properties of individual monosaccharides and theirderivatives 22 9(i) Aldopentoses, 229 - (ii) Pentuloses, 233 - (iii) Aldohexoses, 234 - (iv )Hexuloses, 241 - (v) Aldoheptoses, 244 - (vi) Heptuloses, 247 - (vii) Octose sand higher aldoses, 247 - (viii) Octuloses and higher ketoses, 24 7

g. Isomerisation and degradation of monosaccharides in basic media :saccharinic acid formation 25 1

h. The action of acids on monosaccharides 26 2i .* Oxidation of monosaccharides

27 0(i) Oxidation at the reducing group : the aldonic acids and their derivatives,270 - (ii) Oxidation of the primary hydroxyl group : the alduronic acids andtheir derivatives, 278 - (iii) Oxidation at both the reducing groups and th eprimary hydroxyl groups : the aldaric acids, 287 - (iv) Oxidation at secon-dary hydroxyl groups : the dicarbonyl monosaccharides, 290 - (v) Oxidationat both the reducing group and secondary hydroxyl groups : keto-acids o raldulosonic acids, 298 - (vi) The ascorbic acids, 301 - (vii) Oxidation wit hglycol-cleaving reagents, 30 5

2 . Functional derivatives of monosaccharides 320a. Glycosides

32 0(i) Occurrence ; nomenclature ; physiological significance, 320 - (ii) Synthesi sand methods of preparation, 323 - (iii) Interconversion of anomeric glyco-sides, 337 - (iv) Alkali-sensitive glycosides, 338 - (v) Acid hydrolysis o fglycosides, 34 0

b. Monosaccharide ethers

34 5(i)* Methyl ethers, 345 - (ii) Partially methylated monosaccharides, 346 -(iii) Properties of methyl ethers, 348 - (iv) Trityl ethers of monosaccharides ,349 - (v) Other ether derivatives, 350

c. Cyclic acetals and ketals

35 1(i) Formation, occurrence and conformation, 351 - (ii) Reactions, 36 o

d. Anhydro derivatives of monosaccharides

36 2(i) The glycosans, 363 - (ii) Epoxides, 367 - (iii) Other anhydro sugars, 37 7

e .** Esters

37 9(i) Carboxylic esters, 379 - (ii) Ortho-esters, 392 - (iii) Sulphonate esters ,396 - (iv) Phosphate esters, 407 - (v) Borate and phenylboronate esters ,414 - (Vi) Nitrate esters, 418 - (vii) Sulphate esters, 419 - (viii) Carbonates ,422 - (ix) Thiocarbonates, 426 - (x) Phenylcarbamates, 43 1

* With the collaboration of Dr . C . H . BOLTON .** With the collaboration of Dr . J . M . WILLIAMS .

f .* Functional nitrogenous derivatives of monosaccharides 43 2(i) Glycosylamines (N-glycosides), 432 - (ii) Monosaccharide oximes, 437 -(iii) Phenylhydrazones and related hydrazones, 438 - (iv) Phenylosazone sand related compounds, 440 - (v) Other nitrogenous derivatives, 446

3 . Amino-sugars 448a. Synthesis and methods of preparation

449(i) Ascent of the series, 449 - (ii) Descent of the series, 450 - (iii) Fro mepoxides, 451 - (iv) Cyclisation reactions of dialdehydes, 451 - (v) Replace-ment reactions of sulphonates, 453 - (vi) Amination of nitro-olefins, 456 -(vii) Rearrangement and epimerisation reactions, 456 - (viii) Miscellaneou smethods, 45 7

b. General properties and reactions of amino-sugars 460(i) Reactions with acids and bases, 46o - (ii) Oxidation of amino-sugars ;oxidative deamination reactions, 465 - (iii) Elimination reactions, 469 -(iv) Acylation reactions, 470 - (v) Alkylation ; glycosides, 473 - (vi) Reduc -tion of amino-sugars, 476 - (vii) Determination of amino-sugars, 47 6

c. 2-Amino-2-deoxyaldoses 47 8d. 3-Amino-3-deoxyaldoses 484e. 4-Amino-4-deoxyaldoses 49 2f. 5-Amino-5-deoxyaldoses 494g. 6-Amino-6-deoxyaldoses 495h. Diaminodideoxyaldoses 495i. Aminoketoses 499j. Nonulosaminic acids 500

4 . Deoxy-sugars 500a. Occurrence, detection and general reactions 500b. Synthesis

502(i) Terminal deoxy-sugars, 502 - (ii) 2-Deoxyaldoses, 505

c. Biosynthesis 508d. Individual deoxy-sugars

50 9(i) Deoxyaldopentoses, 509 - (ii) Deoxypentuloses, 514 - (iii) Dideoxy-pentoses, 514 - (iv) Deoxyhexoses, 515 - (v) Deoxyhexuloses, 522 - (Vi) Di-deoxyhexoses, 524 - (Vii) Dideoxyhexuloses, 527 - (viii) Trideoxyhexoses ,528 - (ix) Deoxyheptoses, 528 - (x) Deoxyheptuloses, 52 8

5 . Branched-chain monosaccharides

52 9Nomenclature, 529 - Determination of structure, 530 - Synthesis, 53 1

a. Branched-chain derivatives of tetroses 53 4b. Branched-chain derivatives of pentoses 53 7c. Branched-chain derivatives of pentuloses 53 9d. Branched-chain derivatives of hexoses 53 9

6 . Thio-sugars 54 3a. Occurrence 54 3b. General properties and reactions 544c. Methods of preparation

549(i) Nucleophilic replacement of terminal sulphonyloxy groups etc . by sulphurnucleophiles, 549 - (ii) Via dithioacetals and their equilibration with thio-glycosides, 550 - (iii) By mercaptolysis of ester derivatives of aldoses, 551 -(iv) From poly-O-acylglycosyl halides via isothiuronium salts etc ., 553 -(v) Replacement of secondary substituents, 554 - (Vi) Opening of epoxid erings with sulphur nucleophiles, 555 - (vii) Via episulphides by ring -opening, 556 - (viii) Thermal rearrangements of xanthates etc ., 559

* With the collaboration of Dr . C . H . BOLTON .

d . Individual thio-sugars 559(i) Thioaldopentoses, 559 - (ii) Thiopentuloses, 561 (iii) Dithiopentoses ,561 - (iv) Thioaldohexoses, 562 - (v) Thiohexuloses, 565 - (vi) Dithio-hexoses, 56 5

7 . Unsaturated monosaccharides 566a. Glycals or r,2-dideoxy-l-enoses 567b. 2,3-Dideoxy-2-efOSCS 57 3c. 3-Deoxy- and 3,4-dideoxy-3-enoses 578d. 4-Enoses (non-terminal) 58oe. 4- and 5-Enoses (terminal) 580

8 .* Isotopically labelled carbohydrates 58 5a . 14 C-labelled carbohydrates 58 6

(i) Biological methods of synthesis, 586 - (ii) Chemical methods of synthesis,587 - (iii) Methods of degradation, 589

b. Tritium-labelled carbohydrates 59 2c . Deuterated carbohydrates 59 4

Chapter 24. Oligosaccharides, Polysaccharides and Related Compounds

G. O . ASPINALL, E . PERCIVAL, D . A. REES and M. RENNI E

1. Oligosaccharides 59 6

2. Disaccharides and related compounds 599a. Hexosyltetroses, C 10 H 180 9 60 3b. Pentosylpentoses, C1oH1809, and their polymer homologues 60 3

(i) Ribosyl riboside, 603 - (ii) Arabinosylarabinoses and arabinosyl arabino -sides, 603 - (iii) Xylosylxyloses and xylosyl xylosides, 604 - (iv) Xylosyl-arabinoses, 60 5

c. Deoxyhexosylpentose, C11H2o09 606d. Hexosylpentoses, C11H29010 6o6e. Pentosylhexoses, C

11 H 2o01o • • • • 6o8f. Hexosyldideoxyhexoses, C 12 H2209 609g. Deoxyhexosyldeoxyhexoses and deoxyhexosyl deoxyhexoside ,

C12H 220 9 6o gh. Hexosyldeoxyhexoses and hexosyl deoxyhexoside, C12 H2201o• •

61 oi. Deoxyhexosylhexoses, C12 H22010 • • • • • • • • • • • 61 1j. Hexosylhexoses, C12H22011 . Reducing disaccharides 61 2

(i) Glycosylglucoses, 612 - (ii) Mannosylmannoses, 617 - (iii) Galactosyl-galactoses, 618 - (iv) Galactosylglucoses and glucosylgalactoses, 621 - (v )Mannosylglucoses, glucosylmannoses, galactosylmannoses and mannosyl-galactose, 623 - (vi) Glucosylfructoses, 625 - (vii) Galactosylfructoses, 625 -(viii) Fructosylglucose, 626 - (ix) Fructosyifructose, 626 - (x) Otherhexosylhexoses, 62 6

k. Hexosylhexosides, C12H22011 . Non-reducing disaccharides 62 71 . Dihexose anhydrides, C 12 H 22011 63om. Diketose dianhydrides, C12 H 2O 010 63 1

* With the collaboration of Dr . B . E . STACEY .

n. Glycosides of polyhydric alcohols 6 3 3(i) Pentosylglycerols, 634 - (ii) Pentosyltetritols, 635 - (iii) Hexosylglycerols,635 - (iv) Hexosyltetritols, 636 - (v) Hexosylpentitols, 637 - (vi) Hexosyl-hexitols, 637 - (vii) Hexosylheptitols, 638 - (viii) Dihexosylglycerols an dtrihexosylglycerols, 638 - (ix) Aminodeoxyhexosylglycerols, 638 - (x )Aminodeoxyhexosylpentitols, 638 - (xi) Hexosylcyclohexitol, 638 - (xii )Dihexosyltetritols, 639 - (xiii) Dihexosylpentitols and related compounds ,640 - (xiv) Dihexosylhexitols, 64o

o . Nitrogen-containing disaccharides 64 o(i) Disaccharides containing one amino-sugar and one neutral sugar residue ,641 - (ii) Disaccharides containing two amino-sugar residues, 643 - (iii )Disaccharides containing amino-sugar and hexuronic acid residues, 64 4

p. Aldobiuronic acids 6 4 53 . Trisaccharides 6 4 5

a. Reducing trisaccharides 6 45(i) Trisaccharides containing one constituent sugar, 648 - (ii) Trisaccharide scontaining two different constituent sugars, 651 - (iii) Trisaccharides con -taining three different constituent sugars, 6 5 3

b. Non-reducing trisaccharides 6 5 4c. Nitrogen-containing trisaccharides 6 5 7d. Acidic trisaccharides 6 5 7

4 . Tetrasaccharides 65 8a. Reducing tetrasaccharides 65 8b. Non-reducing tetrasaccharides 66 oc. Acidic tetrasaccharides 66 1

5 . Oligosaccharides from human milk 66 16. Polysaccharides 664

Isolation and purification, 665 - Determination of structure, 666 [1 . Hydro -lysis, 666 ; 2 . Partial hydrolysis, 666 ; 3 . Methylation, 667 ; 4 . Periodat eoxidation, 667 ; 5 . Determination of molecular size and shape, 670]

a. Pentosans 67ob. Hexosans 672

(i) Celluloses, 672 - (ii) Starch and other polysaccharides derived fro mD-glucose . Glucans, 677 - (iii) Polysaccharides derived from D-fructose .Fructans, 686 - (iv) Mannans, 688 - (v) Galactans, 689

c. Polyuronides 69 0d. Complex polysaccharides 69 2

(i) Neutral group, 692 - (ii) Acidic group, 695 - (iii) Amino-polysaccharides ,700 - (iv) Bacterial polysaccharides, 70 3

7 . Teichoic acids and related compounds 70 6a. Teichoic acids 706b. Other polymeric carbohydrate phosphates 70 9

8 . Glycoproteins 709a. Glycoproteins of animal origin 709

(i) Submaxillary gland glycoproteins, 709 - (ii) Blood group substances ,710 - (iii) Glycoproteins of human plasma, 711 - (iv) Egg albumin, 71 1

b. Glycoproteins of bacterial origin 71 29 . Glycolipids 71 2

INDEX 715