Thesis {be Hm: Dogma of M. 5.

«Qt-"mi

nag;

‘-

IV“? 313.5134 STAKE; Si‘iiE’E

LLu
Parvin Medhat

1958

(THESIS

f’I
.‘ ‘ #—

LIBRARY ‘

Michigan State
University

 

Rita-7:332! u: )31p'11-’!i:.11.36.3537:

v:
" l

T! ITRIGWIG AG!”

0'4

1%:

Inflin $349th

A 2’ 62313

Suttdttad to the 5:93:00]. far Adrianna Vii-ram.“ Stu‘iies of flicking-Ln
Strata valved-sitar 02' My! Culture and Ahmad {Balance in
partial 1" lfil'ment of the requirements

for {he éf‘éjrfifi cf

Irieegrv'rrtuas'i ‘ of Cheri stry

was

r‘o"' .‘r‘ :a" '.-“‘\» n ""3“:
. . :. 1~ ‘ . - - 1;
fl ‘th «‘ ‘M u? 3'" - zu-

‘E‘m anther risks: to exg'reu her sinners Appreciation to 3:. Jam:
0. Snack, Jr., fer hi: inmaimtion. iatemut, gala-fiance and mum“
Martinghrmt the courts at $1.13 «may. Sim 3130 wish" to thank thc
Governumnt of {Kim for the scholarship which mask 1% zenith to an!"

on this study.

Eamcm "3!! <3? 91...:n,Y-.‘.3:=‘<=‘r;§£

12:1'5‘34; 1*1-5E1931'I‘3 ACID

By
1' AMI: 5.396. int

Submittsd t9 the ichanl for Advnncaé Graduate fltudicl o! Etchigan
Stake finivarsifiy of Agriculture and Agiliad flaioncc in
gartial fulfillment of the raxutranautn
tar fins éegree of
EUVEFTR Q?*‘i;lfi*3;

misinmm of Chemistry

1933

Aygrovrd _*

I'm-v11: $40th
Page 1

9! A”! r[0:-.1
nae: J'- N- .. a)

(1.. t, u‘}; its "é‘ 9\‘« V ‘I fix; ...‘(I .S
,1 '1 l .i. .y. ‘7 I .5' " 9.Y‘vl '31 I ‘0. ~.‘.'

729.3%: ;.’.'.:',“'£ :41} kHz)

‘I‘ha rates nf ale-wage 1r; garioczia acid of the two ctarbob-m-mrbu
times is ZL'}:~;-.;iycaro:se hive hem inveatigmm by a mound. which final”.
c: rat-31m: out the rmctiun in the Q‘I‘GSBHQO of large nous”: of ILL-.511”:-
055 am} determinim; the ceucantrminna of fox-ma MM and {amuldahydo
i-rmfiucsd. '3“er rate of emission of he ham: between C; and ‘32.? but he.
{mm-t. to be ng-toximtely five Hum grmter than that of the clan.
batman £32 and 33 at 3’3". N 763° the rate of the fora-w: reaction was

observed. to be nearly ten times grahtar than that of the lunar'

a- «£171 .3 L. V ..\ a
f1 1. {I 1'
ti4 . 0000000....000o00000000
"'1 1"“
git-Lu*‘4‘IQOOOOOOIIOQOIOOIOOIIIO
Eifftiul O 0 o o o o n o o o o - o o o c o o c o 0 .
""r-ar {WW}.
'4$\-}‘-o‘d»-" ‘3 O O O O O a 0 O O O o O 0 O o I O O o I O O

Irefitritinn of it: mun-rd Gurus 0f Enrzg'alemhyaia
Cencantrutian Verena Auaurnwn¢a . . . . . . . . . .

"zuxity at the fib—Zlyaerosfi . - . - . . . - v - - ' ° '
l-tfiifldifl. 3H31L1CXiiiifiginn Of Wi—iycerSO o o o o o o o

Setnrminntlen cf tlyexrl in tea karioaeta-uL-dlyasroaa
Venetian Fixture by fryer HhrOmutrogrmphy . . . . .

-.:‘.:;.;r- n: t"'!'. “31' ‘-’f".:-.'.* Y“
.7,- « ‘1'.- :~5.‘~.,-.' IJA’WJ O 0 ‘ . . . . . . . . . . . . . . .

I??? 7%"? H 74 3’31“}!

The: ulmwew by yarimflic acid: a! afirbazi-to-mtrhen Ennis between car-
bon Mama which may either oxygen atom. (as hyébfi’fll groups or at car-
bnnyl Earrings) or se-aina gmups, me first Macaw-reread by if<i-'.11=.;r$adol in
1938. Since its Manon-3w, this rwctirm has found mmuo appllutlohl
in Quantitative lanterzetntatmn: and it im- been and oxt‘slfll} Md no.
caqsfully for hivesugr‘tirm of variant "natural problem- of tho “sari.
Since tho (inningmnt of these hygienic” bus but: rec-nil: “flung.
this mire-fluency: will be manna to «emission of th- mmtlos and tho
mahani 2:1 «:4! the Malia-park rnacttrm.

flu first lreaimo kinetic study of ;.erioaau axial-anon was men-10¢
out on pimcol (beams; of 1:- onnveniamiy maaaureé rmction rat.) by
lrico and Email}. Fri 09 and Kmll observed that £311! raecuon IDLIOII
simple sac-3nd orfiar nuances (tint order in genteel and first ordor in
parlar‘zmfl. 7’11er :11 as found that the value at the second order cannula!
Vftarion ewe-"$13 with this pH of the ranctian mixtni‘e. In an 8616 ”:11“
this rf‘to 63:23} at was [nun-j to he :iirmfily jumportiomel to tho 11700303
inn cwncentrxtian; in 12- 91c mafia it We Itmgertiemd to tea square not
of the ttyoiriixirio ion mncentmtion.

Trice and Eire-9.11“ axial-10$ out nadir-.1- axwrimanta with ethyl-no 3).}.
col. and g3. and. mmvolohexone 51.360). 3-. Ho 043331.191 Vermuon 1::
recs: with fix“ I“: fem-.4. in the rwcti on o: “risque with the-ea mbstancu.
“a the said side, the at“ con-4mm for ethylene glycol mu hand to be

esnaxttmily intiapamiant of the 1:5. fin the bean side it was rnugizly

p~ro;..artiemi to the hydrogen in ”floatation. or the inure. at tho
hydroxide ion Mncantmtion. with roqoot to tho cyoiohoxm 31:001.,
m an and [non fennel that gig-cyclohoxano glycol is oxidized nor.
retrial; than in the Wimmr. Ta erg-.1312: this observation they oug-
gostml n biesolocuiar inversion mechanism involving the {omtion of a

cyclic dinner of periodic acid (initiation 1). Such an intamcdiato M

P \c/’ " 3} I \G-G-l‘i “ i ‘0’")
.3- ma- 3+..— 1 t - ‘34-- -
55492,:- , ' l 1‘ + 23—4, 0!! f I >10ufi‘.’ 4' I. (I)
ma ce-o“ o—o
/\ A " V

Men :r'rnvi-‘muiy irrigated by Mingus who noted that perioéio mid. 11k.
lauzi tatrnfiscotnta, would get an a commutation count. Fanatic: at
such an outer s'mruld moaned most readily that) thc two byviroxyl W
are 3L3. 3211: Men of an intermediate: Master has been generally no-

sey-flea by they writers in tho fiolsi.

’

h ”investigated the wrioaata-othyleno 511ml reaction to.-

Duke
vie-”wt later ans“: found that the: Kinetics of thin rot-action mat to O1-
;lnin-ul by either of tam macimniwm (I) the first order damped“.
of the patients-glycol amylase; as the wt» data-mining stop, or (2)
direct oxidatian of the glycel by wax-10:12:.“ (first order «at in period“.
and in glycol) in whia‘n fanntinn of 9m mummuctiva zerioriato-glyoel
00213191 is a returnibla 316i. rez-‘ction. Furflsmmra, mm found that
tho rate of thin rmcticn is nearly iniayaniaut of Mirage: 1011 «once:-
tmtion in till 3;?! name of ‘5 tn 7. in avian to emits-1n the absence of
a dflfiflndfimy of mt. on pi?! antler than c-mzii tiom. Duh. later refund?

to a mantis}: of “winters! tn than affect that lwrimgen ion cestniytin 1!.

3
this range in errant by deuterium Mai-mum or H5106 to tho react!”
gm“, flung.

In an after-t to obnsrvu tho dioct of matter). mbttitution on tho
rat-.(ztian Nata and tn mierzltrznfl the WM} Offuct of bring“ in. In
tho “riotinto-guimcai unctim, Bruit! and Eule‘fl‘llI mus-ted wt 3 kin-tic
invoatimtion of that ;oria<intn oxidation of attainno £13061. pmpyim
giyc'vi, em and miremimc 31ml” triuthflotlvlm MI I“
flannel. mil-m and hugjrin fauna that all of the" subttaneu. cxupt
flannel. behaved flail-Friar tn stir-31mg gang}, unich it ta ray that thy
data were in aeeorflnnec with the following anhreeaicnt

fluid .10!

I“; '* gtiyehwlzcyalio ixatsnz.liatn—-+1;rmiuctt (2)
'90: the yimonl retention. than and 5115,1211!) ”mm that tha exudation
3:00am: thrmurh a cyclic intammuato. Eon-tar. in this inatmwo. tho
rate humming: no}: in the famtion o! tho can-.119: batman tlm glycol
and fortunate. 'i‘hit sienna.“ of mminx {amnion mes attrihntsd to
steric hindrance! by then (nut methyl grant: which (one the hydrant).
etrcsugt out of u {wanna oritntntion {or mrdimtian with wrioflato.

5‘3!» primate oxidatinn a! cnrbohwmtm in "Lima 8 they). mo—
tien on account of that rclyhmatiomiity at then flflHFIWQ mick my
lz-fin'ait tho occurmnca of hath meagatiflvo and contamitifl razotionu.
Fence. ”mgr-ma to It camels” imiei‘ttflndlm of that oxiziatianu Mt
been mime and Iatmowhfit limited.

IHV$9$1;;:’F-‘i?n of the :mchanim of the g-qrioéretn oxiiati-Jn of eel-bo-

hydrates hm berm Image-trim 31 the rapid rites of Hwy 05' £31m” twiafi.

I.
fin“, (Brigham? found flmt it In: nearly 1133:6131“. in mam. flu
this. of fin initial Imgpt of several aldou-poriofiflto ruaetionm
at in! towns-awn and mnmntmtionun-w fanning. mo Me's in pn-
iodmto ti an. A. m:- as u in imam such rain but now: been noun-
etely determinn-d.

In spin of th- rayidiw with which yuriodzzto aiuwu cautiona-
in carbshydmim, them: at. one»! slot phase: in tho mu“. ouch“.
of than substances. For own“. this behavior has: been noted for tho
pariadio acid ozitmuons of iL-glucoum'n and D—xyioscu, both 0! shin):
am quite new in their final. stages. However. than 01" ”as. do not
involn direct rmctioun batman periodic acid and the auburn“. but.
11mm, may result tron tho slam»: of tho hydrolysis of intanudiato
prmhmts famed in m. iniiial oxidation» Thus, 501m}: and $11.11”a
hand that tn. mt. detox-Buzzing any in (no has: put of Sh. nautical:
of 9.5111003. with itOYiOdkl“ it the hydrolysis of bfhfon'wlan-mclrou
('i‘sjnmtion h) which in fan-sud in the Iciosian of the bow: henna c). and
(2.2, 0:? and 63. and C3 and $34 (Eqvmtian 3). mac-pt and Mid firmly

OH

H!)

+.

B {)9}!

 

man o $ 233(123 «o are (3)

0

H3011 tic-Nail
l

H3 8820?]

K3&0 3W
0 slot -
{6-0-68 + $3.20 ———-> 322303. + Ewan (h)
(acidic
wean conditions) $11203

catahiinhsd this fact hr isolation a! 2aG-formw1-fl-glyoero:o from.D-
glances-pariodio acid rawatiun mixtures.

Information abnut tho relativs rates of periodatfi oxidation 9! tbs
bond: between 31 and 3?, an& hatwaan C?'and C3 of kstoaas have bait
available Iran tbs time a! thn first apylicatiuno of tho Halaprndo ro~
aotian to thnae subatnncuo. For examilc. tbs consumytian of n.55 mole.
of pear-13:19: ta, inst-am! of 5.0 moi”, by 1 ml. of fructose (:3.er in-
diaatel that thn ruto of cloavngn cf tha 01-32 bond traced: that of
saisuinn of the 62-33 band. it tho rates of thas- cloavagms wet: equal,
the cansumption or psriofinta per-uni. of fructose would ha “.5 noiou.
sine. glycoiio maid formad by oxidation of tho 63-53'hond aquatics 5)

is nat nttadknd by periodnta at any significant rate.

fag-nu ring“
0!) 603!
. ~+~ + ’
mi}?! ———’ 35M ( 5)
E?CH 4303
l
Effifl HCOH
GHéOH GEEQH

Euvertholcss. thaso data tram hates. oxidation: previdc only‘qnal-

itntivo knowiadgn of the relativa rates of ths periodato oxidfitian of

6
tin. ciifffamnt kiwi: of mm; win-An airbag/amt”. It is only very r.-
‘ cantlg that some {rt-ogre" bun beam made in the quantitatin dotemiufl-
ti an of thus efri'mztm. G'nristanarenq art-tied cut an invmtiggmtion of'tho
rfilrativn mtes 0f clatmg-a 01’ the two c'irb-':n«to-c"..-rbl'an 19:33:23,. in '51..-
glyoamm by a teammate which involved large ration of tho canmntntion
of “Emilycvrou to flat of }.ariodic acid. Chri stem-um orzerivmood can.
9i fi‘icuity in obtaining; turn-main? ”Mata—44H armtly batsman of in-
sufficiently rflfid mixing ni‘ than tar-whats. ‘siotwitaatfindim; this. hi.
data indicated that, at 2‘30. the ciafivs‘wa of th! 61-32 bond is approx-
imtsly tin times; as that no t'm-st of the {32—133 band (for intact m..-
glycomss) o

Emoten‘tiy. fiuhmrsu has c==rriefl out a similar invastigatiam in

which lug! oxmlu of (alumni toi (duicitoi) and mutual tel var. oxidilod
:1 t}: yfirifrdtttfio mkmrt'u emerirwnts indicate yrrai’erantial oxidatiu
of um-Elycnl gram-s, mince than gaa'iactitoi oxidatian affordad princi-
ynny n tetroaa (T-tiqmation 6), whet-mu the manual tor-:ction saw mill:

(glyaemu (‘iqmltian 7).

{than}! (fizz? H
H 7?! KM
5173'??? ____) + 13m + Him (6)
I l
'r'flgfi '1.) 35! £130 H
o r 'I"
ii {ET-i - {I’M 729$}!

mean swam: (3’5?sz

 

"Grip 1. in)
tan-2;! > 2 H 2‘03 (7)

— + .
‘—
J

Hail 3}! M7333
E391!
13‘? 7??) ii

The pmamt invmtiqstian we rm attszapt to utomi than work of

fizristmaan on the flinpzijofiraum-parioriio acid £00611“.

RT 11:: II- :' Z‘J’rr‘d.

At-rf:.r-=tns. A Beam-mu model B synctmrhotameter mguiyyti with
Cora: cells was mad for 0:310:31 dmni ty mat-smmmnta. A Minnow!»

utnd Renal-inn pH meter was mad far all ficiLh-zae titr-‘stions.

Chev-2i $13. $le flingiycorou czay..loyad in than experizéants UM
tithe: prapared according to tho “Organic Syntheses Procwiuro'xu Or can
a Nutritional Biodlmaiailt Cougars tirm pmduct. ’Fhio parimjia acid In
a pro-met of than :1. Frederick Ska-in: mas-41223.1 00.. Sodium bicarbonato,
ammonia}: acetate, }..otaonim iodide, araaninua acid and muiwu aoetntn
warn all mp. grade. fan hyfim'q‘isusine ‘ruriroouorizh and nontgrlnmatono

var. Eastman Kodak boast grads.

13'rgl‘,nr9filgn of ggg-m,-srd Gun-veg of Emmi-alfie‘sgfia «“vrmvzeutratinn versus
—r ~_ “ m _ —-—-— w “m

W

 

 

fibanrhrlzfl. E‘ho pro'cednn and to determine formidawdo van the on.
3910101qu by flash”. Rambling! ho‘xmmt‘zwlena totrmina nu hydrolyzed

In tact-amended by Hmhydanls

in order to prawn a formula-mm min.-
tion of known concentmtion. The standard our" In: cnnqtnxctad Irma
five-paint plot: according to the following; procndnru Tho rug-ant

was prawns by :ii univing :? gram foam». waigjzts of arts-‘Ennitm acetate.
0.05 min of auntie acid. and 0.02 male of acetylac-etnnq in mats: and
dilutim: the solutinn to a '0'in of 1 liter. Five millilitqn of this
rang-mt and 5 miliilitnn of a salutinn (of known concentratinn) contain-

115?; nag mare ”yin 3 micrograms nf tonmldehy-ie par millilitnr were mixed

and allowed t9 stand for 5 hours at roam tmwrature. Fina anal-trance

i
Ira-o than manure-i at 3.3.2 milliniamno Sig‘fiiiitt a blank chic-11 mu man up
by mixing aquni 79.11.21“ of res-agent and water at than 33-12% ti?» that tho

solutian of foraaidahydo and reagent were aimed.

Itiritz 95. V6: ‘='?I..--"si"a:er9§_§_. ”:an yurity of thc ZTIL-giycaroas ml

"

   

checked by oxiirtion rim ”rig-510 acid. the millilitfir at 0.2 M gun".
039 was 3&de to 1’5 milliliters 9f 0.01.35 2+3 periodic acid. "I’E‘dt ma-
ticn mixture ms aliomd to staid for four hours at room tompamturo

and me: than nautmiixed with «can tcdiw bicarbamatn. To this mix-
tn." mu added I? millilitnrs of 5 percent potauium iaéida. This was
followed imadiataly by thu addition of 10.00 milliliter: of 0.13 I!
scdium uraauito. After 1‘5 minutes. the cues: nadiw araanita ms
titrnutwd with 0.03%? 1*! ioziina to a starch 05.1 paint. Tho {ax-10:351.“

cr-nstnx-,,.tiznra Ir: a (2*? percent of the thenratiml aummt for game-craze.

:«yiwgiic said: {‘ifi'i datvinnfing :L‘Imfifij'ceiqsgt. “£110 o-muuntrntion of fert-
iodic acid mm kept mzmtant in an of the" experimnts but the ratio
of tho initial glycerosc concentrntian to that of rariofiiu acid was
wrisd from 1.95 to 10.0. The a".1:1uiratsd atsmzmt of Fifi-.WMOO WI
pinned in tha mite: tact-ion oi‘ a swuisd mixing; Vectal and dinmlvcd
in 2‘3 milliliters of nutter. Yin milliliterg of 0.“ if 123140316 acid
'MJI pincer! in tho cantral inaction. This mail»; 133391 In: and. by fix.-
ing a glass tube 3 cantinowra ;:zi;_;h in that center of a i“C-millilitar
urinmmyar flask. 283' filming the .m513cast. Ami garioaiata solutim
in th- segmratg soci‘mzs, it V1.3 mniblo to bring: that: into 0:;nili‘brim
with tho tharzmutat before maxing mm in ashlar“ ne'txt'ly inst-mummy

mixing; by mum-1m: tim- 11...“.- 3k.

10

I’m two sown-ans rem mg in the thermoawt far 1 hour balm"
mixing, In ordnr to allow for mammriwtion of ma crystallim excl“
dinner, which I: inmymlo of ramtimz I1 £121 parloélo acid. 0!) shading
In aqueous 001131911 $233 diner dissociate! into the flammab-altimzh
nut omylctely. kf‘hir tilting: the. solutions, m. reaction none}. In.
allowed to remain in ‘ho thurnoutut f0; lfllrhllf hour hoist. carrying
out t2.» analyses.

Than farm'ldelwdo mneantrretiana in “was 1&1me mo 119:9qu
by thus 35292115 m-tlcmd. 'i‘hn fen-:10 scisi um: {19thqu by annual of
then rmactiou mixture with sodium midi-0:51:10 for total acidi‘y (lulu ‘h‘
lino-oyartdhd Becm'an 3;?! meter t6 cieteraina the and point) and I!) Inb-
trfictinfi' than Lmown mxmmlont of indie amid from the tabs]. acidity.

In order to indicate than offset of ”hum-lat”. on tho relative rat—o

of oxide-jinn of the two bands the flame IKL-fil'imn“ Were repeated gt 20° C.

'0‘

9'5 5.“. -_ ' «‘ i; . . - - '0.»_,~1 .-.f.- .- Tw 1: q ~ 1" r- .
“It bamum‘ 9i . . £9. E"! ”410.....t9- «3.119930% v.33 sung

v— fin"

 

 

Vizzmw 151 w C‘nrmnrttqugflgi. Twnty munnam at 0.25 1-! mn-
gxycsrom cult-film m-s mixed rigidly with 5 milliliters of 0.34 35 par-
103.10 acid 30113193. This rmmtlan mixture ma allow-ad to "and for
tang-m4! hour to wears amid-19:10:: of tho reaction. An amass of
stanfir’tr‘ii araanna 1:031LG solution and 2 ruiliillt-fl’s of 5 yercent potas-
8111:: Smith salutizm var-9 than aai‘idezi to this mixtura. After 15 921mm“.
0.5 (gr-«m of hyaroxfizmias hydrochloride and 1 5mm of sodixm fiestas“
warn mam 8.22:1 the raw. um; :42er an allowed. to stand 1‘»:- 34 imam.

M the and of $1.13 Mam, this mixture m... setup-Jed with main! unload.

11
and cxtrnatad with «13%. 3$~nilliliter iortlons of ethyl athst. th
cw'bined extrncu were dried nvtnrniggm over anlvgiroul so“. «an».
The other was Man ramvsd under mom in order ‘0 avald ovuhmung
‘hn rosidug. 9kg residua In. dissolved in 0.2 miikllitar of 23‘s: and
u fan draps of the solution ware gluced on a strip of Whatmaa KO. 1
tiltar gapor. ?ho solvent used fur 13pm: ohrnnatogruphy III tubul-
sszemratml R-I’AGIMQIo After allowing the solvent to :1“ for 18 bun,
tha 33:13 In. dried in thc air and sprayed with n 5 purccnt ooluttan of
nickeloua chlorlds. 0n oxyosing tha resulting damp chruuntogrnn $0
Antonia gm. the m ckelnui ,glyozimo emails: an. 91-3er M I idle! ”oh
This chrmmmgnn rm c'r.::g..::4r»e;i with ammo:- yuan rat W in th-
umma any tram a knawn solutINn of algaxnl. Th» xosi‘lonn of the 0pc}:

on the OMMtOfiP-nfitfi from the has: and unimarn mixtures. are Manuela.

'F3‘Li§?fif?'3 my ”5353!? 7’13

1?; . . . .
As nhristsnaen’ noted, the taxation of pariouic acid vita nL-giycar-
039 in the prauanca of nxccaa glycaroaa (Iquutlan 8) is capable of giving
Y9“)
'—‘* HEW) H + 354.0

vicre 0 "H 2 I
my} 33/ .3..va + «3:393 2

.1..—

3‘61““£Q\~*
('3 mt :gfi *

(3)

l

{icy-J}
«If ‘5‘, 3 rrI),,H
“'93

informatian about £39 rates a! sciasien of the two ourbnn-ia-aarhou bands
in hia subatrfite. ”braver, in this system therg are {Gut grinnipul pro-
ducts, inraic fluid, formnldghyfiq, glycolaldohyua and glyaxal, in addiiiOI
to india Hold nnfi unrwfictqd glyceroas. Such.» mixture obviously riquiran
five indapandent analytical methods tar determining ita cauyositiou.
ffig formic acid profiuced is detarflinahla by titratien cf the reactien
mixture for iatnl guiding end bv sihurzotix' *he knnwn an.1leent a!
ioaic acifi frnm this tntal. Eh; farmmldehyfio ennaflntrntian can be
measured with high percisinn by tbs Egan procadurels. But, ei in. proaaut,
thirty-.3 are. no diract mag-thaw for fit!) Antarmimtion of glyoml. glycoialdo-
hyda and fiL—glycernso in such mixturqn. Xanea, the enmglcto analysis of
this nystaa cauld an: be employaj for datermining tbs variaus oxidation
retas.

Neverthelesa,_ths daisrminatinn of formic acid and farmaldnhyda

onnsnntrntinns ware unafal in dwtnrmining thg relative twigs a! oxifiation

1!
of the boni- in giycurom. When the reaction of giyoarou uith periodic
sci-5! goes to emailation, the ratio of the mnemtrutian of formic laid

:rnriucsi to t‘z‘z-t of fonxillaivde is equal to P (.iqwzti-rm 9). On the -

f}! + 2 mh——r 219302}! + one!) + 2 i", (9)
CHZGH

othar hand. 1!, by nude-ling axes“ glycamso. the reaction can In rutriotcd
to the oxidation of intact giyceroao molecuiu only. the ratio of for-i.
acid to fomxldohyda harem-ma tho ratio of the rat. at ociuimi of tin
«11-3? bond to th'tt of the hand between 132 and (:3 (31 I he). Obvimnly.
thin ratio mxy be greater tit-n, ion than, a: «ml to 2.

In the present} car-printouts. on inorganic; the ratio 0! Dip-31:00:03.
to periodic: no“! in the oxiéatian aixturn, tho ration of fomio acid to
toner-Adah?” a; branched a liuiting min. Canal 1:08:11 to 1+ £| 30? (‘2qu I)
and tag} rnximatoly equal to 10 at 20° {Tab}. II). this meant that ill
giycerom) the oxidrztinn of tho 1mm between the albhydo group find tho
secondary carbon is u‘mmt {dun timan {mater than 010%"?ng of tho how!
bet'n'avan t'na sac'vnzwry cz-‘srbnn and tits primary carbon. ’i'ha prenm of
mmxiz‘iixed $130911 in such “action mixturu ma «353$in by converting
this substance to its dioxins and identifying gm. derivative h: paw
chroma togrn; hy.

It is martin noting first marque—aim the tangemturo of thy glamorou-
psrimiio acid reaction mixture profinon a gmtnr increase in tho rat.

a! the slower roaction. This Eucharist van expected, since. if the

1k

1) : ‘t‘ts ‘52:}
1- . .u‘u‘e .

Sffwct f

O

incrmaaing th Ratio 9f tht Initial Gancmntratian of
33.};ycarnsa tn that at hatiniiu Acid fit 30°.

“1 ‘ *1 v—r ~— r v—— r ‘v' «OI-- u-rwv’. “*GWHWWWOWOthw—memw
.‘m ..... m“

 

 

 

 

 

 

¢_"~.. _.....t~....-..- -__.._
Initifil pvriofiia Kaugiyuurnao finnnantrhtian of fiancantratisn of
acid cancantrhtian ‘fnrmlc acid formnliahyflo
ouncantrfitian ”aldwlllter grnducad rrofincod
finlwa/ther ‘ “ales/litwr‘ Hales/lite!

 

a.a83 0.0 ' n.0u26 3.2;555
ruff??? {3.14 65.1233. 3.91535
(5.08%; (3.2 (“”00 0.531352
9.689 0.2 0.6d03) 0.51343
“ - 37"" ”-1 MW“ 0.019163
0.033 2.1 $.0596 0.fi17h6
9-“*3 0-03 w.a5aa $.03h36

0.953 {1.05 {fr-06%;? 0.03536

15

’i" “L, V: II

Rifect 0f Inornhsing thq Ratio of the Initial Canctntrfltion of
vLmfilyceroso to that of reriodie Acid at 20°.

 

 

 

 

 

 

Initial periodic HL—giyeuross Concsntrntion of Concentration of

acid concentration ioralc acid formaldnhydt

gnncentrstion Holaa/lit&r graducsd {roaucod

Helga/liter Raina/litar - 5.393/11tar
v.n¢u a.h 3.3736 0.3968h
fi.fi£3 n.2 0.373% 0.01fl72
0.393 0.1 0.07%8 $.01???
c.075 G.1 0.0743 0.01900
0.033 0.05 0.0672 8.03372

0.x?8 3.05 0.0622 0.037hs

M

h _—_._ v—wv

16
fiactinti an energy is lower for clear-2.5+! of the 31-03 hand than it 1.
far clmwge of tiny 232-03 bond, tins rate of tho latter reaction should

be affect“? morn by a chart-ge- 1n tam; erntura tint: the-Lt of the tamer.

EIELI 23a???
(1) 3'Ill’lmua Lo 0513‘th rfind. 131; “QIlqp‘g); Bidlo .83. chin"
I o o .l J o_ .. Q .
{frana23. h #3. b3} (ifiafi).
(P) Bobbitt, J. M.. fifivnnuaa in $2rbohy£rvte Guam., 11. 1 (1956).
(3) fricu, C. {:0 tin-l W. Frail, 010‘“. Gildfi. SCCQ. 6". 2726 (1333).
(u) Erica, 3. c. anfl x. gnall. J. Am. Chem. fiac.. 6%, 552 (19%2).

(a) Grieg-o, 3., Sltmoar, $03. Reforuar. gEI Huturw Eurburg. 62, 25
f1?3#).

(6) Rukl, Y. no. J. Am. Chem. Tcu.. §?, 3954 (1347).
(I) make. F. a. uni v. c. Bulgrin, J. Am. Ch... 506., zg, 3303 (198%).

{3} Kfitnre, w. A. in H. flilman “firgenic Chnmigtry‘, Vol. 1?, (Few Yark,
Raw York) Jenn Riley and 3033, Inc.. (19fi3) G? E. 1?.

(9) ihriatwnaan, J.. Ih.D. Thnsls, Vicglgnn Btwte Univaraity, East
Lansing, fiichignn, _1950).

(10) Karrnr, 0., and K. P. riacnlor, Helv. Cain. Acta, L1, 766 (1%35).

(11) SL‘DGK Jo Co. 2.1:... and R. A. "fibriflt. final. Shell}. a; 101‘? (l35h).

(I?) Schoyt, 0., and E. Wild, Chem. Ber., E1, 1371 (123%).

(13) $chw‘r3. JO Co. v?- Cbsm. 800.. ??D (12‘57). I

(lhfi fittgemann, E. J., H. L. fivana, H. tags and E. F. Sabraaflar.
“Urganic Rgnthusae“, 0611. vol. II. p. 30%. (flaw $crk, Ea!
Vork} John Wiley and $nns.

(15) Hugh, J., Biochem. J. {Lnn¢cn). fii. klé {1?}3).

(16) xac?.ydan. 3. 2.. J. 31.1. Sham-. £15. *0? (lq*5>'

CHEMTS'T‘B‘? mm mm
Date Due

MY LIBhAI-i

 

Demco—293

HUI/1W

1:;

WHO.
EH6
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mgr/3m

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12

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