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R etrospective hTheses and Dissertations *1..!)%0!,-%.2+-.*)!-4!-!-) % F ollow this and additional works at:$

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#%.'!+*-%.*,2*,(*,!%)"*,(.%*)+'!-!*).. %#%,!+%-..!! /R ecommended CitationM ittts, Ada Eleanor, "Reaction of glucose with some amines " (1943). . 13725.

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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!

In

Charge of Majoi^ Work

Head of Wjor Deparliment

bean Iowa State

College

1943 Signature was redacted for privacy.

Signature was redacted for privacy.

Signature was redacted for privacy.

UMI Number: DP12859

INFORMATION

TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted.

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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
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ProQuest

Information

and

Learning

Company.

All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300
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|\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 R V, H fi .R 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

I c"sa

I moM

I IOCS

I H0OH

I HOOH

I mon I H 1 I EC 01

I BOGH

I HCOl

I ISOH

I HGOl

I E \

EH-C-H

HCOH E R

HCOfi

I HOCH

0 HOCH I

HGOH I HG - I HCOH I H I HCOH

I HC^ -

I HCOH

I B

Syn and Antl Imlso

Structure ~ and

^-Pyranoside

Struetur® R

H I \ HCOH

HOCH 0 ni-J

I HCOH i HCOH I H B

I h-c-h-h

l\

HCOH 1

HOCH I BC- HCOH

1 HCOH

I H and £-Furanoside

Structure

- 5 - (c) R®arrang"ffient H ECH

I G»0

I H00E

I mos

I BGOl

I BCOB BOB

BO-C,

I BOOB

I HCOB

I HO B

I N-R BCOB

I B OB w

. RBC-0 B

I BOCH

I BCOB

BG BCOB

I 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

C%-Gg%-K-C

HCGH HGOH p-Tolui(3ia"-d''Glucosl<3e a.p*

X15®

C. CHg-CgH^-SsCH

HCOH I HOCH

I HCOl

I HOOH

I HCOH

II "*^chiff 's

Baa©

Strueture H

1 B 1 CHgCgJ^HC^

COH 1 OaO HOCH 1 1 HOCH

HCOH 1 ICOH j

HCOl 1 HCOH

1 HCOH

1 1 HCOH

1 1 H 1 H

III ^aaol Structur© IV *K©to Structure H

CHsCg^S-C^-C / OH

HOCfi

I HCOH

I Jw

I BOOB

I E H

HO. /C%MCgH^GHg HOCH

HCOH

BG HCOH

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 asquotesdbs_dbs14.pdfusesText_20