S533 RELATIONS BETWEEN ROTATORY POWER AND STRUCTURE IN THE SUGAR GROUP PART I INTRODUCTORY ARTICLE AND ARTICLES 1 TO 10 By C. S. Hudson ABSTRACT In 1909 a beginning was made in correlating the structures of sugars with their rotatory powers by the author's appUcation of Van't Hoff's hypothesis of optical superposition to the sugars and various of their derivatives. This method of correlation was extended in numerous subsequent articles to the lactones, the amides and phenylhydrazides, the compound sugars and glycosides, and many other opticall}' active substances. The method and its results and the new experimental data obtained in the course of these researches have come intO' extensive use in the fields of organic and stereochemistry. In the present work the author's various articles have been systematically arranged and republished^ either in full or with some condensations. It is hoped that the orderly presenta- tion of the subject mil assist research workers in the use of this new method of investigation in stereochemistry. CONTENTS Fafir« I. Introduction 244 II. A summary of the author's earlier researches on relations between rotatory power and structure in the sugar group 245 1. Two rules of rotation in the sugar group (the isorotation rules) derived from Van't Hoff's hypothesis of optical superposition 245 2. An empirical relation among the equilibrium constants of the mutarotating sugars 249 3. A systematic nomenclature of the alpha and beta forms of the sugars and their derivatives 250 4. The rotatory powers of the glucosides 252 6. The rotations of acetyl derivatives of the sugars 254 (a) The rotations of the glucose penta-acetates and the methyl glucoside tetra-acetates 254 (6) The zinc-chloride method for transforming sugar acetates to isomeric forms 257 (c) New ring forms of sugar derivatives. The four isomeric penta-acetates of galactose 260 (d) A correlation of the reactions for acetylating sugars- 261 (e) The rotations of the acetates of the alpha and beta forms of methyl xyloside, glucoside, and galacto- Bide 262. 241 242 Scientific Papers the Bureau Standards of of i voi. ti II. A summary, etc. —Continued. 5. The rotations of acetyl dcrivativcrs of the sugars—Continued. Page (J) Optical superposition among the acetylatcd deriva- tives of xylose 263 {g) The rotations of the beta hepta-acetates of methyl maltoside and methyl cellobioside 263 (Ji) The rotations of the beta hepta-acetates of maltose, cellobiose and lactose 265 {i) The rotations of the alpha and beta methyl gentio- biosides and their hepta-acetates 266 6. Indirect measurements of the rotatory powers of some alpha and beta forms of the sugars by means of solubility experi- ments 267 (a) Description of the method 268 (6) Experimental results 269 7. Some numerical relations among the rotatory powers of the compound sugars 272 (a) Sugars of the sucrose group 272 (6) Sugars of the trehalose group 277 (c) The related rotations of lactose and cellobiose 279 8. A relation between the chemical constitution and the optical rotatory power of the lactones of the sugar group. The lactone rule of rotation 280 (a) The hypothesis 280 (6) Test of the hypothesis 282 (c) Application of the theory to determine the con- figurations of the sugars 284 {d) Proof of the position of the lactonic ring 286 (c) The stereochemical configurations of the sugars fucose and rhodeose 289 9. The phenylhydrazide rule of rotation (Levene (1915), Hud- son (1916)) 292 10. The amide rule of rotation 297 (a) The rotatory powers of tartaric and tartraminic acids and tartramide 299 (6) The configurations of the active mahc acids 299 (c) The configurations of the active mandelic acids 301 id) The rotatory powers of the amides of several alpha hydroxy acids of the sugar group 301 (e) The lactone and the amide of methj'l tetronic acid_ 305 (/) The amide of a-mannoheptonic acid 308 III. Relations between rotatory power and structure in the sugar group__ 309 1. The halogeno-acyl and nitro-acyl derivatives of the aldose sugars 309 (a) Classification of the halogeno-acetyl and nitro-acetyl derivatives of the aldose sugars as alpha or beta forms on the basis of their rotatory powers 314 (6) Classification of various acyl and halogeno-acyl derivatives of the aldoses 316 (c) The calculated rotation of i3-chloro-acetyl glucose.. 322 (d) The calculated rotation of 1, 6-dibromotriacetyl glucose (aceto-1, 6-dibromo glucose) 322 (c) Calculation of the rotation of bromo-acetyl gentio- biose 323 — Hudson] Rotations and Structures of Sugars 243 III. Relations between rotatory power and structure in the sugar group Continued. Page 2. The halogeno-acetyl derivatives of a ketose sugar (ci-f ructose) — 324 (a) The rotations of beta-fructose and beta-methyl fructoside 324 (6) The rotations of the two chloro-acetyl fructoses 325 (c) The rotations of fluoro-acetyl and bromo-acetyl fructose 326 {(i) The rotation of beta-tetra-acetyl methyl fructoside. 327 (e) The rotations of the two isomeric penta-acetates of fructose 327 (/) Discussion of the conclusions 328 8. The biose of amygdalin (gentiobiose) and its configuration. _ 329 (a) The relationship of amygdalin to iso-amygdahn and prulaurasin 331 (6) The rotatory powers of the glucosides of the amyg- dalin group 332 (c) Calculation of the rotation of the biose of amyg- dalin 333 4. Two isomeric crystalline hexa-acetates of dextro-alpha- mannoheptose 335 (a) Experimental part 338 (6) Summary 339 5. The chloro- and bromo-acetjd derivatives of arabinose. The nomenclatm-e of alpha and beta forms in the sugar group. Some derivatives of 1, 6-dibromo-acetyl glucose, gentiobiose and maltose 339 (a) The nomenclature of alpha and beta fonns in the sugar group 341 (6) The calculated rotations of Fischer and Armstrong's dibromo-acetyl glucose, etc 345 (c) The rotation of alpha-bromo-acetyl gentiobiose observed by Zemplen 347 (d) The calculated rotations of some acyl derivatives of maltose and gentiobiose 348 (e) Postscript 348 (/) Experimental part 350 ig) Summary 351 6. The rotatory powers of the alpha and beta forms of methyl d-xyloside and of methyl Z-arabinoside 352 (a) Preparation of the alpha and beta forms of methyl d-xyloside 353 (6) Preparation of the alpha and beta forms of methyl Z-arabinoside 354 7. The methyl glycosidic derivatives of the sugars 355 (o) The rotation of the terminal asymmetric carbon atom in the methyl glucosides, galactosides, xylosides, and arabinosides 357 (6) Comparison of the rotations of various methyl gly- cosides with those of the respective sugars 358 (c) Methyl d-lyxoside 359 (d) Beta-methyl d-isorhamnoside 360 (e) Calculation of the rotations of the forms of d-isor- hamnose 362 — 244 Scientific Papers of the Burecm of Standards [ voi. ti III. Relations between rotatory power and structure in the sugar group Continued. 7. The methyl glycosidic derivatives of the sugars—Continued. Page (J) Methyl fucoside 362 (gr) Methyl maltoside and its hepta-acetate 363 (Ji) Ethyl maltoside, ethyl glucoside, and the value of aEt 364 (t) Methyl lactoside and its hepta-acetate 364 0) Methyl Z-sorboside 365 {k) Summary 366 8. Some terpene alcohol glycosides of glucose, glucuronic acid, maltose and lactose 367 (a) The menthyl and bornyl glucosides and the menthyl-glucuronic acids 369 (6) Menthyl maltoside and menthyl lactoside 371 (c) 6, rc-anhydro-Z-menthyl glucoside 372 {d) The crystalline lactone of c^-glucuronic acid 372 (e) Summary of results 373 9. The rotation of the alpha form of methyl gentiobioside recently synthesized by Helferich and Becker 373 10. The chloro-, bromo-, and iodo-acetyl derivatives of lactose- 374 (a) Experimental part 376 IV. Table of rotations of pure substances which have been measured in the course of these researches 378 V. Index 381 I. INTRODUCTION In this publication there are reprinted in Section III. pages 309 to 378 the first 10 articles of a series entitled '^Relations Between Rotatory- Power and Structure in the Sugar Group " which were originally pub- lished in the Journal of the American Chemical Society. As an intro- duction to them there has been prepared a summary (Sec. II, pp. 245 to 309) of the author's earher researches on this subject, given as far as possible in the form of quotations in order that the present publication may be used as an original source of reference. A table of the rotatory powers of those substances which have been purified and measured in the course of these investigations (Sec. IV, pp. 378 to 379) and a thorough subject and substance index '(Sec. V, pp. 381 to 384) have been prepared as reference aids. It is hoped that the orderly presentation of the work may assist research workers and advanced students of organic, physical, and biological chemistry who may be interested in carbohydrate chemistry. It is recommended to such students that they read E. F. Armstrong's ''The Simple Carbohydrates and the Glucosides" or H. Pringsheim's ''Zuckerchemie" before studying the present publication. Grateful acknowledgment is made of the painstaking assistance that has been rendered by a large number of coworkers whose names will be found in connection with the description of the substances, some old and some new, which they have carefully prepared and — Hudson] Rotations and Structures of Sugars 245 measured. The investigations have been carried out as projects of two Federal departments, those from the years 1909-1919 having been performed in the Bureau of Chemistry of the United States Depart- ment of Agriculture, and those subsequent to 1923 having come from the Bureau of Standards of the United States Department of Com- merce. II. A SUMMARY OF THE AUTHOR'S EARLIER RESEARCHES ON RELATIONS BETWEEN ROTATORY POWER AND STRUCTURE IN THE SUGAR GROUP This summary has been prepared in 1925 as an introduction to the 10 articles on this subject that are republished in Section III of this monograph.