Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1943 Reaction of glucose with some amines Ada Eleanor Mitts Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Biochemistry Commons, and the Plant Sciences Commons Recommended Citation Mitts, Ada Eleanor, "Reaction of glucose with some amines " (1943). Retrospective Theses and Dissertations. 13725. https://lib.dr.iastate.edu/rtd/13725 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. NOTE TO USERS This reproduction is the best copy available. UMI l1 REACTIGH OP GLUCOSE WITH SOSl AMINES by A. Eleanor Mitts A Thesis Sul»aitted to the Gradiiate F&Qxiltj for the Degree of DOCTOR OP PHILOSOPHT Major Subjects Plant Cheaiistry Approved! Signature was redacted for privacy. In Charge of Majoi^ Work Signature was redacted for privacy. Head of Wjor Deparliment Signature was redacted for privacy. bean Iowa State College 1943 UMI Number: DP12859 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. UMI UMI Microform DP12859 Copyright 2005 by ProQuest Information and Learning Company. All rights reserved. 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Box 1346 Ann Arbor, Ml 48106-1346 0Ii3£l |\4 G 9 av - ii - ^ J} TABLE OF COSfEK!I?S Page IHfKODOCflCl 1 ElVIll OF LIflRATORl 7 Ammonia Derivatives of Glucose 7 l*Aminoglucose 7 2>Aminoglucose 13 3-Aminogluoose 14 3>A]Qinoglucosd 15 Phenylhydrazine Derivatives of Glucose ..... 16 Hydroxylamine Derivatives of Glucose ...... 33 Aliphatic Amine Derivatives of Glucose ..... 34 Asiide Derivatives of Glucose 39 Arcsaatlo Amine Derivatives of Glucose 39 Amine Derivatives of 2-MethylglucGae ...... 59 IXFESIMMf AL . 62 Fhenylhydrazine Derivatives of Glueoae ..... 62 Preparation of the ^hydrazide reported by Behrend 64 Preparation of the ^hydrazone reported by Behrend 68 Preparation of phenylbydraaine derivatives of glucose corresponding to derivatives of corn syrup dextrina . • 71 Hydrolysis of phenylhydrazine derivatives of glucose and laaltose .... 78 rn 10 - iii - Pag© Aliphatic Amine Derivatives of Glucose 79 Preparation of glucoaylalkylamines . • 79 Catalytic reduction of glucosylalkylamines « 90 Potenticaaetric titration of the H-alkyl-d-glucaaines 98 Hydrolysis of glueosylalkylaminea 98 Attempted AsMtdori rearrangement of the gluooaylalkylamines 106 Jjmonia Derivatives of Glucose 107 Preparation of l-arainoglucose 107 Hydrolysis of l-aminoglacose 108 Preparation of 2-aminoglucose *«....«• 112 Attempted preparation of the p-toluidide and the K-tolyl-d-3^o- 'glucos€utiine fr(^ E-aminoglucose .•••.• 113 Aaide Derivatives of Glucose 114 Preparation of the 1-acyl derivatives of loaminoglucose 114 Hydrolysis of H-acetyl-l-aminoglucose . .. 115 Attempted condensaticm of acetamlde with gluoose and acetobromoglucose . « • 117 MTGrntle Amine Derivatives of Glucose ...... 119 Preparation of aryl-H-glucosides and H-aryl-d-isoglucosaaiine 119 Hydrolysis of the H-glucosides •••*•.. 121 .teine iHsrivatives of 2-Methyiglucose 126 Phenylhydrazine derivative 126 Phenylosazcaie 127 Iv « Page p-5?oluidide of 2-Biethylglucose ••••«»• 128 Attempted rearrangement of p-toluidlde , . • 129 DISCUSSKM OP HiSULfS AND COHCLUSIOHS ......... 152 SUMMAiy ....... ........... 145 ACESOWXEDGMEHtS ......... ...... 147 GIfED ................... 148 1 IHfRODUCflON Although a considerablo amount of work h&a been dotne on the nitrogen derivatives of sugars, the literature regarding a great many of these derivatives is very confused# The reason for this confixsion is quit© evident when It is realized that eaeh of these derivatives laay exists theoretically at least, in a number of isomeric structures. $he following diagram shows the possible structtares for the compounds formed by the reaction of an amine, Rl]^, with glucose: (a) Addition H fi R ' .R V, H-C-OH HOC-H-H BCOB HCOM HOCE HOCH HCOH HCOH HCOH HCOH HCOH KJOH H 1 oc « and ^-Addition Compoimds of Aldehyd o~S trueture - 2 - (b) Water Bllialnatlon H 1 I \ E R c«sa EH-C-H I I moM EC 01 HCOH HCOfi I I I IOCS BOGH HOCH 0 HOCH I I I I H0OH HCOl HGOH HCOH I I I I HOOH ISOH HG — HC^— I I I I mon HGOl HCOH HCOH I I I I H E H B Syn and Antl Imlso ~ and ^-Pyranoside Structure Struetur® R H\ I B I h-c-h-h l\ HCOH HCOH 1 HOCH 0 HOCH I ni-J BC- I HCOH HCOH i 1 HCOH HCOH I I H H - and £-Furanoside Structure - 5 - (c) R®arrang«ffient B H I N-R ECH BOB w .OB I RBC-0 G»0 BO-C, B I I I H00E BOOB BOCH I I I mos HCOB BCOB I I BGOl HO BG I BCOB BCOB BCOB I I B B Eeto Structure and l3-.2,6-Puranosld« StruGttu>« (These may also exist in the pyranoside structure#) fhe keto iscaier and the 2,5-furanoaide compounds that exist \ in equilibrium with it were obtained when the N-glucoside compound of certain aromatic amines was heated in the presence of a trace of acid or ammonium salt. The postulated mechanism of this rearrangement, named after its discoverer, Amadori, has been advanced by Kiihn and Weygsuad (77) in the following diagrams H B CHg-CgH^-SsCH C%-Gg%-K-C HCOH I HCGH HOCH I HCOl I HGOH HOOH I HCOH II p-Tolui(3ia«-d''Glucosl<3e "*^chiff's Baa© Strueture a.p* X15® C. H 1 B1 CHgCgJ^HC^ COH OaO 1 1 HOCH HOCH 1 1 HCOH ICOH j 1 HCOl HCOH 1 1 HCOH HCOH 1 1 H H III IV ^aaol Structur© *K©to Structure H H /OH HO. /C%MCgH^GHg CHsCg^S-C^-C HOCfi HOCH I HCOH HCOH I Jw BG I BOOB HCOH I E H VI *<-2,6-Purajioslde Structure 0-2,5-Furanosld0 Structure ~ HI.p. 152® C. ^"Postulated intermediate compounds not isolated. No generallBation has been made in the literature, but the data obtained from the different glucosyl amines indicated that the ease of effecting the rearrangement depended upon the relative negativity of the amine and the stability of the gluooside to hydrolysis. •To ccaaplicate the study further, the addition compounds and the 1-glueosldes not only were converted from one struc­ ture to another in aqueous solution, but also were dissociated into the free amine and glucose until an equllibrlua between the glucosyl amine, glucose and the amine was reached. fhough ccaapounds that have been classified as differed widely in cheniical properties, the ccmtpounds foiTsied by the reaction of these amines with glucose may be considered as derivatives of glucose anaaonla. The differences in the glucosyl amine obtained depended upon the R group substituted the asiffionla. A great deal of work has been done on the glucosyl amines, but the investigations have been isolated studies of a particular amine or group of amines rather than a comprehenaive study of the reaction of glucose with amines. A tremendous amount of investigation has been done on the reaction of glucose with phenylhydrazlne, yet the literature is very confusing concerning these derivatives. The oxlmes of sugars have been known for years, yet their relationship to 1-aminoglucose was often not recognized. Recently the synthesis of vitamin Bq instigated a thorough study of the glucosyl aromatic amines which resulted In elucidation of "• 6 -• the Aamdori rearrangement. The literature concerning the afflmcmla, phenylhydrazine, hjdro3Eyliuaine, aromatic and aliphatic amine derivatives of glucose has been reviewed in order to establish a basis of comparlsoa for the reaction of the different amines with glucose. - 7 - BEVIEW OP LITERATURE Sine© th© reactions of ajnmonia and the substituted amines with glucose have been investigated as isolated studies rather than ae glucoayl amines differing only in the substitution of the nitrogen, it was necessary to make the review of literature on each type of glucosyl amine. An effort will b© made later to correlate these compounds as derivatives of 1-aminoglucose and to show that the differ- encea in the properties and reactions way be e:^lain©d 1;^ the variation of the substituted group• AffiKonia Derivatives of Glucose l-Aainogluooae Glucose aiHtncmia was first investigated by Lobry de Bruyn and Franchimont (84), who observed that glucose exhibited an unusual degree of solubility in anhydrous ethyl or n^thyl alcohol containing aBUBcaaia gas. The rotation of the solution of glucose in the §nimoniaoal methyl alcohol decreased as the glucose reacted. After several days small aggregates of crystals precipitated out of the viscous solution. Upon analysis this compound was identified as an isoiaer of chitose amine or S-aminogluoose reported by Ledderhose (78) and of the isoglueOSamine made by Emil Piacher (29). The properties of this new isomer differed greatly from the known amino glucoses in that it was very labile to acids, although the free amine was quite stable even in aqueous solution. This stability in water was demonstrated by the fact that the specific rotation of an aqueous solution changed only from +19.65® to +13.6® in ten months. The investigators were unable to prepare the salts of this base. This fact was par­ ticularly noteworthy since the hydrochloride of 2-aminoglucose was quite stable.