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0 H I T 0 8 E
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to th e
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C E R T I F 1 0 A T E.
I ’ certify that Archibald Bracléhaw ■
/ Grant has spent eleren ,terms at research
v/ork under my direction, and that he has
fulfilled the conditions of Ordinance No.
16 , (St.AndrewsJ and, is qualified to;submit
. the accompanying thesis for the degree; of
' : jEtii,D. : :. % ./ . :. : . . . ' .
St. Andrews. Direlffor ofIResearch.
a A R E S 8,
I matrlouleted In the University of 8t* Andrews
In October 19%. end followed the rooognlead conroe of
study In the Foonlty of Belence for the degree of 5.80*
In 1936 I peGOod the Geeond Science Degree
excmlnctlon In the anbjects of Physiology end Ghemletry
end In June 1939 g re d n o te d w ith F lr o t Glees
B.Sc#,
Honoure In Ohemletry*
With the eesletence of e Oemogle Reeeercl)
G ch o le re h lp th ro u g h o u t eeaelone end IghO'^l
1939*^40
I carried out in the deportment of Phyalologioel
Ohemletry research wor%t which wee Interrupted by a
period of service with H. M* Forces, During the
oeaolon 194S"*W I was awarded a Rehabilitation Buraary
by the New g&ealand Government end reoumed my reeeeroh
programme, the résulté of which form the aubject of
the présent thesis.
writer here ezpreeaee his gratitude to
D r. A. hynd fo r h lo k in d ly In te re s t end v e ln a b le
erltlelem throughout the course of thlo Inveetlgetlon#
sn^enks are also tendered to the Oernegle Truet
for t3ie Onlveroltleo of geotlend end to the New %eelond
Government Deportment of Rehehilltatlon for the owerde
of Beeeoroh Seholarehlpe which heve enabled the writer
to undertake thle work#
0 0 M
H T. K. te... JS
ïæ .R om ?Q gion.
hl&tors'
Previous of cîüitose «mâ ohjeot of research,
WmOBBTIOAI,.
3
fjujyyey of essperimentsl ?esuîts anfl tSieoretiosl
âlsüusaion.
mO jji’opeptioe of 'fWWWii MA'##*#»'1*1 AN l.a
p re p e ra tio n o f d"*mr8blnooG% one fro m o h ito s e 75.
s o la tio n .
P re p a ra tio n o f fro m o h lto e e s o lu tio n . 76.
Gome p x 'o p e rtie o o f o h lto o o s o lu tio n # 77*
Bonrio o b o e rv ü tio n e on th e fo rm a tio n o f d"*erebino80A e 77.
in
ohitooe nolutloa,
im <m w «ww «w iw* *»*
Attemptod prGi)8^^ion of cryotolllne cbitome dorivativee, o
The 2:WimtrophenylhydroaonoG of gluoooo and mannoae* 7g#
Tho o r y s ta llln o o h ito o e 2 :W in ltro p h e n y lh y d ro & :o n e # 80.
The y ie ld s o f o h ito s o ^ a W in itro p h o n y lh y d ra z o n e 83#
o b ta in e d under vo% *ying e x p e rim e n ta l e o n d itio x w .
A tte m p te d m o th y la tlo n o f e h ito s e S tZ ^d in ltro p h c n y l'^ 8Aw
hydredone.
A tte m p te d bensoy lo tio n o f c h it ose 85
phony IbydreiaioAe#
Aeetylatloa of the iSAdlnltrophenylhydres&oaeo of 86
gluooee end ehitoae#
A tte m p te d p re p o m tio a o f e o h lto e e e th yllû e m e 88
#
eondeneetloa product
A tte m p ts 8 t o o n d e a o a tlo n o f e h lto e e w ith ooetone 89
and
benseldehyde#
90
Aeetylatloa of ehltoee*
D e a a o y lo tlo a o f o h lto e e # 91
methylotion of ehltoee*
A tte m p ted a lm u lte n e o w d e e c e ty le tlo a end 93
mothyletlon of the ehltose aeetyl derivative#
Attempt at eo)%lete methyletlon of free ehltoso* %
Attempted preporotloa of methyl ehltoolde. 95
The extent of glueoeomlae hydrochloride @6
deamlaetlon by the method of j^eehmeieter end Toth#
The e x te n t o f glueoaem lae h y d ro c h lo rid e deem laatiom 97
with mdltm nitrite reploolag silver nitrite#
Ai epprmilmote oomperleon of the ehltoee content of 98
eolutlone of glneoeemlne hydroohlorlde deemlneted
with (1) Silver nitrite*
(8) Sodlim nitrite#
The preparetloa of ^methyl ohltoaide* oymp, 99
(G raph 1 ).
Méthylation of ^methyl ohitoeide* eyrnp by
(1 ) H m m rth ^e m ethod* iOO
(2) Purdie^e method# 102.
sydrolyels of fully methylated ohltoae. 1(%,
The c r y s ta llin e sem iearbesoae o f trlm o th ^ l 105
eldehydocii 1 tooe#
O x id a tio n o f f u lly m e th y la te d c h lto c e w ith a c id 107
m W alkaline permcngencte solutions (Gr^h 2)#
Bctimatioa of the cimpectod degree of m&aaturation liO
of fully methylated ohitoae#
W e m in c tio a o f 3 th % 6 trlm e th y lg lu c o a a m ia e h y d rc o h lc rld e
cad ieolatioa of «/^-^^methoxy^g'^methyl furfural#
115
The ectioa of 8^ hydrochloric acid on trlmethyl
aldc3)y doch i t oeo #
Préparation of trimethyl eldehydochltooc by the il6
ueuel method employed in the preparation of
methylated eldohydohexcao derivatives#
Ohitoee dlethylmerceptml# 117
Partial méthylation of chltoee diethylmerceptel by 118
the method of Haworth#
Complete méthylation of chitooe diethylmercaptel 118
by the method of Freudeaberg*
jHydrolysie of trimethyl chltoee diethylmerceptcl 119
end ieoletion of the resulting trimethyl aldehyde**
ehitoee in the form of its cryetclline eemiocrhesone#
OKldetlon of fully methylated chltoce with nitric 120
Odd end iaolotion of the roeultiï^g trimcthyl
chitonlc ecid#
Uneucceeeful ettempta to pmpcre a cryetelllne 122
derivative of trimethyl chitonic ecid.
Preperetion of trlmethyl chitonlc acid by methylet^ 123
Ion of eliltonic acid*
The ethyl ester of chltonic acid# 123
The metliyl eetcr of chi tonic acid# 12k
