ANTIOXIDANT PROPERTIE S OF ETHOXYQUIN AND SOME - IFFO

178 Pages·2004·5.49 MB·English

ANTIOXIDANT PROPHRTTES OF

ETHOXY QUIN AND SOME OF TTS

OXIDATION PRODUGTH

A Thesis
presented for the degree of
poCtoR OF PRILOSOPRY
im the Fooulty of Soicnee of the

University of St Andrawe

by

SNORR THORTASOR, Bee

November 1987 United College of St Sulvatdr
and St Leonard, St Andrews
‘CERTIFICATE

I certify that SNORRT THORTSSON has beeu onguged in research at
the University of St Andrews, has fifilled the conditions of
‘Ordinance Generel No 12, and is qualifled to submit the accompunying
thouis in application for tha degree of Qoclur of Philosophy. He was

aduilted under thie Ordinance in January 1984,

Pioaask

T cortity that the followiny thenis is based on the resully of research
carried out by me that it is my own composition, amd hus not

previounty been presented for a higher doyree.
ACKNOWLEDGEMFNTS

I would like to express my thankw lo the following:

Profossor

Gunsione (St Andrews} and Ge BR, Hardy (torey
Rensarch Station, Aberdoou) for their help and supervision, and Dr

J.C. Walton for his help concerning the ESR spectroscopy.

‘The Tnternstional Assoniation of Fisk Meal Manufacturers

WAYMMM) for financing this project, and De

SM, Barlow for useful

discussion,

‘The Univeraity of St Andrews and the Tory Renearch Station,
Aberdeen, for providing the research decilition in whtoh the work was

curried out.

The technical ata of the Chewistey Department of the
University of St Andrews, and the stalf of the Torry Research
Station, for their help during the project. Special thanks go to Mr

J. Murray for kis help concerning the HPLC and radicisotope work.

T algo like to thank Nina Casta for prostreading my thoviv und

Cuthorlne Fisluy for the trping.

My grootost thanks go to my fowily and frieado for their

constant support and oncourayement.
ABSTRACT

Ethoxyquin (h2-dfhydro-G-othony-2,2,¢-triwathylguinotine UM,
athoxyquin mitroside (Lt), 2,8-dinydre-2,2,4-trinethy!-6-quinolone (111)
nd 12-dibydro-G-hydraxy~2,2,4-trimethyiquinotine (IV) were propared
‘and ponitied in order ta study their antioxidant properties in fish
meal and/or oll, (also commercally wvailabie) and Ibi wore aquatiy

effective in fleh meal, but THT and iV were batter in oll than J and 1,

4 AlN Initiated moths! aoleate autoxidation, the order of
efficiency In terms of the stotebiometric factor (n), using BET ws a
standard, was IV > T> se > U4. On the other hand, HE gave very

Hee inbibition in thie eystom.

Ja fish meal and oll, 1 was converted to Il and to a 1,8'-dimar
(WP. The game products were formed in tort-butory oxldation of Is
Thy nitromide (Ui) mas sino formed trom I but thig was only aoen by
SSR in various otigunic solvents. ft is likely t piay gous role in the

autiaxidert mechaninm of F

The }8'-diner was jsoleted and found to have no antioxidant
Broperties in eit Another reaction product af J, 24-dimethy!6-

ethoxyauinotine wes also prepared. It was found to show nrooxidant

effects ik fish oil,
conrenTs

corti fioste noe rr
doknonledgenents 6. tty ees

Moatract eae on oe

PART

CHAPTER 1 GENERAL THTRODUGTLON 6. -. ”

CHAPTER 2 PREPARATEON AND PHYSICAL. PROPERTIES

DF ETHORYANIN AD SOWE OF 11S DERIVATIVES

Ql whrountion 6. eee

Remulte and Discussion

2.2 Preparation of tahelled and unlabelled ethoxyazin . ++
2. Spectroscopie propertiex of ethoxvauln

2.4 Preperotion of 2,4-dimethyl-b-ethovyauinoline +.

2,5 Preparation of L,2dihydrenf-athary-2,%,¢-trimetiayl-

goluoline-nitroxide

2.6 Praparation of 2,8-dihydro-2,2,4-rrinethyl

quinolone

2.1 reparation of 1,8'-(1,2-dihydrosSonthmye2,2,4-trbmaths]—
autnodine

2.8 Proparation of 1,2-dibydro-§-brdroxy-2,2,4otr]nethy]~
quinoline

APPENDLE 1 HMR epectea

APPENDIX 17 Mase epectra

Page

w

a
CHAPTER 3 SR STEDTES OF RTHOXYAUIN AND SONE OF 17S OxLDetTON

PRONE o oe
BL dmtroditerton ee 2
Results and Diaenaaion
2.2 HSM Spectra of vadinala obtained from ethuyyauin§ -. SD
4.2 SR Specten of wthowyauin itroride ce ewe Ea
3.4 SH Snectra of radicals obtained from 1,2odibyaro-
bydzoxye2,24-Urimathy laine ine and 2,6-dibydre-2,254-
trimethylSeauiwolone re
cuApTER 4 LIVID ANALYEIS noe ee aL
4.1 Intraduetion : a
4.2 Source of experinentel noterin] eo

Results and Discussion

4.9 Batty aold analysis and oil content of flsh aval
AA Effects of satioxidants a 8B
CHAPTER § © ACTOREDATION OF FISH MEAL AND USH OTE =. 2.68
6.1 amteoduction we o oR

Results and Discussion

6.2 Ethoayguiu in fish oile
4.3. Bthoxyquin in fieh meal. a
5.4 Ethoxyguin nitroxide in fish ofle tos ES
5.8 Antioxidant properties of 2,6-dihsdro-2,2,4triaethy}6~

avinetone and U,2-dLhydeo-€-hydroxp-2,2,4-trinethyl=
quinoline oe eye eee ee
6.6 _Effots of the 1,8"-cthexyquin diner and 2,4-dinetayl-

S-othoxrquinoline in oil autoxidation ++ +. eee 88
CHAPTER 6 OFTRATION RNACTTONS OF ETHORV@UIN AND SOME GF 178
ORIDATION PRODECTS ee
$1 Intsoduotion ss oe
Reaults and Discussion
G2 Oxidation seuctious of ethoxranin woe

B.8 GCS wiudiew of resetions of ethoxyquin and suav of ite

oxidation products in {igh oii. 2 + toe

CHAPTER 7 TNHAULTLOW OF A1My INITIATED ADTOETDsT TOS OF
WeTHYL LANOLKATY BY EPHOTT@UTW AND TAREE OF 1S

OnToAPSON exODOCTS 4

TL Intraduction on ”

7.2 Rogues and Diseusaion

CHAPIN & CONCLUSIONS AND DISCUSsIOx coe

PANT 2 RPMRLME TAL

CHAPTER 1 GENEHAL werNOUS os

PRAPTRR 2 PREPARATION OF ETHOLYQUIS AKD SOME OF 17S O¥TnATTON
PRODUCTS oe

CHAPTR 3 FSR STUDIES OF ETWOTYQULS AND SOMK OF J" OKTDATION
FRoMIETs

CHAPEER 3 CTPTD AVALXETS

CWAPTER 6 ALTUKDATLON exvunsMeuTs

CHAPTER 6 OXIDATION REACTIONS OF LIHDNTQCTH aN som OF TTS.

‘OREDATION PROBLCTS

Page

105

ae
CHAPTER 7 INAIRTTTON OF ABN INITTATED AVTOSIDATION OF MBTETI.

MINOLEATE BY BTHOXYGLTS AND THRRE OF ITS GXTDATTON

peonuers noe
RBFEREWIE

PART wwe hoe

PART 2 yee ee eee ee

Live of Figures rans

Mat of Tables.

135
CHAPTER 1.

GENERAL INTRODUCTION
‘Lipid, oxidation

‘Gridative deterioration oan be of great iaportance in products
containing unneturated cantres, Unialuvated fatty aca ranct
non-enzymically with oxygen by autoridation and nhotnoxydenation oF
they may lao bo oxhltaed in enzymis reactions, ‘the moat importunt

oxidation reaction in alin and oll-voritaining products tv utaridation.

Autoridation ia a radical chain-reaction involving three stess:
initintion, propagation and termination.
‘An sllzlic, rosonanoe-stabilized, radical ia formed through

reuctlon of unsatursted compounda (RIX with various initintors (1+).
Initiation Baek oF

An emuipla ia the abslcaction of hydrogen from the disllytic

carbon in Ibnolente.

The linaleste radival then xeacte with oxygen to produce finally a

T™, 13 9. oT
DAR

The initiator can be formed ty direct thermsl dissociation,

mete! catslyain or photolyats, but mort often it ig a product of